- Preparation of unsaturated nitriles by the modification of Mitsunobu-Wilk procedure
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An efficient one-step procedure for the conversion of unsaturated alcohols into the corresponding nitriles by the modification of Mitsunobu-Wilk reaction is described.
- Aesa,Baan,Novak,Szantay
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Read Online
- Radical trifunctionalization of hexenenitrile via remote cyano migration
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A novel radical-mediated trifunctionalization of hexenenitriles via the strategy of remote functional group migration is disclosed. A portfolio of functionalized hexenenitriles are employed as substrates. After difunctionalization of the unactivated alken
- Chang, Chenyang,Wu, Xinxin,Zhang, Huihui,Zhu, Chen
-
supporting information
p. 1005 - 1008
(2022/02/01)
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- Rapid and Simple Access to α-(Hetero)arylacetonitriles from Gem-Difluoroalkenes
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A scalable cyanation of gem-difluoroalkenes to (hetero)arylacetonitrile derivatives was developed. This strategy features mild reaction conditions, excellent yields, wide substrate scope, and broad functional group tolerance. Significantly, in this reacti
- Hu, Dandan,Liu, Jiayue,Ren, Hongjun,Song, Jinyu,Zhang, Jun-Qi,Zhu, Guorong
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supporting information
p. 786 - 790
(2022/01/28)
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- Synthesis of Succinonitrile Derivatives by Homocoupling from Cyanohydrin Derivatives with a Low-Valent Titanium Reagent
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A method is described for synthesizing succinonitrile derivatives bearing alkyl or aryl substituents from cyanohydrin derivatives using low-valent titanium. The active species in this reaction is proposed to be a resonance hybrid of the TiIV nitrile enolate and TiIII alkyl radical.
- Endo, Ryusei,Kishida, Atsushi,Matsunaga, Kazuma,Nagasawa, Kokoro,Takatori, Kazuhiko
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- HCl·DMPU-assisted one-pot and metal-free conversion of aldehydes to nitriles
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We report an efficient HCl·DMPU assisted one-pot conversion of aldehydes into nitriles. The use of HCl·DMPU as both an acidic source as well as a non-nucleophilic base constitutes an environmentally mild alternative for the preparation of nitriles. Our protocol proceeds smoothly without the use of toxic reagents and metal catalysts. Diverse functionalized aromatic, aliphatic and allylic aldehydes incorporating various functional groups were successfully converted to nitriles in excellent to quantitative yields. This protocol is characterized by a broad substrate scope, mild reaction conditions, and high scalability. This journal is
- Hammond, Gerald B.,Mudshinge, Sagar R.,Potnis, Chinmay S.,Xu, Bo
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supporting information
p. 4161 - 4164
(2020/07/14)
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- Scalable α-Arylation of Nitriles in Aqueous Micelles using Ultrasmall Pd Nanoparticles: Surprising Formation of Carbanions in Water
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A scalable synthetic method is described for both the preparation of ultrasmall palladium nanoparticles and their subsequent use in catalyzing an α-arylation reaction of nitriles in aqueous micelles. This method involves the intermediacy of carbanions or keteniminates, which are presumably stabilized by the micellar environment rather than being quenched with water. These Pd nanoparticles are thoroughly characterized. Mechanistic studies using 31P NMR spectroscopy revealed the binding of phosphine ligand with the Pd surface and control experiment confirmed the zero-oxidation state of palladium. The scope of the transformation is demonstrated over 35 examples, including one at 50 g scale.
- Ansari, Tharique N.,Bihani, Manisha,Bora, Pranjal P.,Finck, Lucie,Handa, Sachin,Jasinski, Jacek B.,Leahy, David K.,Pavuluri, Bhavana
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p. 6816 - 6821
(2020/07/16)
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- A convenient reagent for the conversion of aldoximes into nitriles and isonitriles
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For the dehydroxylation of aldoximes with 4-nitro-1-((trifluoromethyl)sulfonyl)-imidazole (NTSI), slight modifications of reaction conditions resulted in significantly different reaction paths to provide either nitriles or isonitriles. The challenging conversion of aldoximes into isonitriles was achieved under mild conditions.
- Zhang, Wei,Lin, Jin-Hong,Zhang, Pengfei,Xiao, Ji-Chang
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supporting information
p. 6221 - 6224
(2020/06/29)
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- Divergent synthesis of isonitriles and nitriles by palladium- catalyzed benzylic substitution with TMSCN
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Ligand-controlled palladium-catalyzed divergent synthesis of isonitriles and nitriles from benzylic carbonates and TMSCN has been developed. The BINAP- or DPEphos-ligated palladium catalyst selectively provides the corresponding benzylic isonitriles, wher
- Hirano, Koji,Miura, Masahiro,Asai, Kento
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p. 12703 - 12714
(2020/11/09)
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- Palladium-Catalyzed Direct α-Arylation of Arylacetonitriles with Aryl Tosylates and Mesylates
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The first general palladium-catalyzed α-arylation of arylacetonitriles with aryl and heteroaryl sulfonates are reported. Pd(OAc)2 associated with XPhos serves as the effective catalyst to facilitate this reaction. A broad range of electron-rich, -neutral, -deficient, and sterically hindered aryl/heteroaryl tosylates and mesylates are coupled with arylacetonitriles bearing different substituents to give the corresponding products in good to excellent yields. Catalyst loading down to 0.1 mol-% Pd was achieved, and 22 unprecedented compounds were synthesized from 43 demonstrated examples using this method. Its applicability with the modification of biological phenolic compounds was successfully demonstrated. The Pd/XPhos system catalyzed the α-arylation and followed by alkylation in one-pot sequential conditions, resulting in the direct synthesis of compounds containing quaternary center- and deuterium-containing compounds in good to excellent yields.
- Yuen, On Ying,Chen, Xiangmeng,Wu, Junyu,So, Chau Ming
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supporting information
p. 1912 - 1916
(2020/03/13)
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- I2/Li2CO3-promoted cyanation of diarylalcohols through a dual activation process
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One-step base promoted strategy for cyanation of α,α-diaryl alcohols has been developed under mild and transition metal-free conditions. This method provides a straightforward and facile way towards the synthesis of β,γ-unsaturated nitriles and α-phenylnitiriles from α-vinyl carbinols and α,α-diaryl methanols, respectively, up to 99% yield. Moreover, various azides and ethers could also be accessed from their respective nucleophiles under standard reaction conditions.
- Hu, Liangzhen,Hussain, Muhammad Ijaz,Deng, Qingfu,Liu, Qing,Feng, Yangyang,Zhang, Xiaohui,Xiong, Yan
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p. 308 - 314
(2018/12/11)
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- Method for preparing nitrile by reacting acetone cyanohydrin with haloalkane
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The invention provides a method for preparing nitrile by reacting acetone cyanohydrin with haloalkane. According to the invention, by using acetone cyanohydrin as a cyaniding reagent, the problems, such as long reaction time, low yield, strict reaction conditions and the like enchanted in an existing preparation method in which highly toxic sodium cyanide or potassium cyanide or expensive trimethylsilyl cyanide is used as a cyanogen source, are solved. The method comprises the following steps: dissolving acetone cyanohydrin in a mixed solvent of a high boiling point dipolar aprotic solvent anda low boiling point aprotic solvent, adding a catalyst lithium hydroxide, stirring at 25-50 DEG C for one hour and then adding a haloalkane for continuous reaction for 2-3 hours; next, adding saturated saline water for washing twice, separating out an organic layer, and boiling off the solvent after drying, thereby obtaining a nitrile compound. The method for preparing a nitrile compound disclosed in the invention is characterized by low reaction toxicity, simple process, easy of operation, low production cost, and a yield of more than 95%.
- -
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Paragraph 0043-0049; 0051-0057; 0062
(2019/08/20)
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- Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides
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The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized molecules is of fundamental interest because nitrogen-containing motifs are found in a large number of life science molecules, natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein we report the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O2 or air. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesise functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Additionally, applying this iron-based protocol, primary amides have also been prepared in a water medium.
- Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Sharif, Muhammad,Kalevaru, Narayana V.,Jagadeesh, Rajenahally V.
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supporting information
p. 266 - 273
(2018/01/12)
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- Development and Utilization of a Palladium-Catalyzed Dehydration of Primary Amides to Form Nitriles
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A palladium(II) catalyst, in the presence of Selectfluor, enables the efficient and chemoselective transformation of primary amides into nitriles. The amides can be attached to aromatic rings, heteroaromatic rings, or aliphatic side chains, and the reactions tolerate steric bulk and electronic modification. Dehydration of a peptaibol containing three glutamine groups afforded structure-activity relationships for each glutamine residue. Thus, this dehydration can act similarly to an alanine scan for glutamines via synthetic mutation.
- Al-Huniti, Mohammed H.,Rivera-Chávez, José,Colón, Katsuya L.,Stanley, Jarrod L.,Burdette, Joanna E.,Pearce, Cedric J.,Oberlies, Nicholas H.,Croatt, Mitchell P.
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p. 6046 - 6050
(2018/09/27)
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- Mechanistic Insight Facilitates Discovery of a Mild and Efficient Copper-Catalyzed Dehydration of Primary Amides to Nitriles Using Hydrosilanes
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Metal-catalyzed silylative dehydration of primary amides is an economical approach to the synthesis of nitriles. We report a copper-hydride(CuH)-catalyzed process that avoids a typically challenging 1,2-siloxane elimination step, thereby dramatically increasing the rate of the overall transformation relative to alternative metal-catalyzed systems. This new reaction proceeds at ambient temperature, tolerates a variety of metal-, acid-, or base-sensitive functional groups, and can be performed using a simple ligand, inexpensive siloxanes, and low catalyst loading.
- Liu, Richard Y.,Bae, Minwoo,Buchwald, Stephen L.
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supporting information
p. 1627 - 1631
(2018/02/17)
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- BF3·OEt2-mediated [1,2]-aryl shift: Synthesis of functionalized α-arylnitriles via the bromination/cyanation/deformylation of substituted deoxybenzoin
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A new sequential, tandem synthesis of functionalized α-arylnitriles via the bromination/cyanation/deformylation of substituted deoxybenzoin has developed. CuBr2-promoted bromination of substituted deoxybenzoins gives 2-bromo-2-arylacetophenne 3. The cyanation of 3 with sodium cyanide (NaCN) generates epoxynitrile. Then, a treatment of epoxynitrile with BF3·OEt2 results in the formation of functionalized α-arylnitriles 4 via a 1,2-aryl shift.
- Chan, Chieh-Kai,Chang, Meng-Yang
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p. 5207 - 5213
(2017/07/28)
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- A process for the preparation of diphenylacetonitrile
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The invention belongs to the synthetic field of organic chemistry, and is particularly relates to a method for synthesizing diphenylacetonitrile by using mandelonitrile. The method comprises the steps of adding mandelonitrile and benzene into a reactor with a stirrer, a condenser and a thermometer; dropwise adding concentrated sulfuric acid at a temperature lower than 45 DEG C; reacting for 1 hour after concentrated sulfuric acid is completely added; adding water; layering; washing the oil layer with water; drying and distilling out benzene; and distilling out a product at a reduced pressure. The method synthesizes diphenylacetonitrile by using mandelonitrile, thereby preventing strong tearing property of alpha-bromobenzyl cyanide which is an intermediate prepared by using bromine. Besides, the method takes use of concentrated sulfuric acid as a condensing agent, thereby reducing cost.
- -
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Paragraph 0014-0016
(2017/03/24)
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- A method for synthesis of diphenylacetonitrile
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The invention relates to a synthesis method of a pharmaceutical chemical intermediate diphenylacetonitrile. The method includes: taking phenylacetonitrile and benzyl alcohol as raw materials, adding sodium alkoxide for catalysis, and under a heating condition, performing an alpha-aryl substitution reaction. The method has the characteristics of simple process, easy operation and high yield. The product has good quality, low price, low toxicity, environment-friendliness, high yield, and high content. Thus, the method is suitable for industrialized production.
- -
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Paragraph 0023; 0018; 0019
(2016/10/31)
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- The Concise Synthesis of Unsymmetric Triarylacetonitriles via Pd-Catalyzed Sequential Arylation: A New Synthetic Approach to Tri- and Tetraarylmethanes
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The selective synthesis of multiarylated acetonitriles via sequential palladium-catalyzed arylations of chloroacetonitrile is reported. The three aryl groups are installed via a Pd-catalyzed Suzuki-Miyaura cross coupling reaction followed by back-to-back C-H arylations to afford triarylacetonitriles in three steps with no over-arylation at any step. The triarylacetonitrile products can be converted into highly functionalized species including tetraarylmethanes. This new strategy provides rapid access to a variety of unsymmetrical tri- and tetraarylmethane derivatives from simple, readily available starting materials. (Chemical Presented)
- Nambo, Masakazu,Yar, Muhammad,Smith, Joel D.,Crudden, Cathleen M.
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supporting information
p. 50 - 53
(2015/07/28)
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- "Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles
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Organic nitriles constitute key precursors and central intermediates in organic synthesis. In addition, nitriles represent a versatile motif found in numerous medicinally and biologically important compounds. Generally, these nitriles are synthesized by traditional cyanation procedures using toxic cyanides. Herein, we report the selective and environmentally benign oxidative conversion of primary amines for the synthesis of structurally diverse aromatic, aliphatic and heterocyclic nitriles using a reusable "nanorust" (nanoscale Fe2O3)-based catalysts applying molecular oxygen.
- Jagadeesh, Rajenahally V.,Junge, Henrik,Beller, Matthias
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- Direct Dehydroxylative Coupling Reaction of Alcohols with Organosilanes through Si-X Bond Activation by Halogen Bonding
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The combined use of a halogen bond (XB) donor with trimethylsilyl halide was found to be an efficient cocatalytic system for the direct dehydroxylative coupling reaction of alcohol with various nucleophiles, such as allyltrimethylsilane and trimethylcyanide, to give the corresponding adduct in moderate to excellent yields. Detailed control experiments and mechanistic studies revealed that the XB interaction was crucial for the reaction. The application of this coupling reaction is also described.
- Saito, Masato,Tsuji, Nobuya,Kobayashi, Yusuke,Takemoto, Yoshiji
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supporting information
p. 3000 - 3003
(2015/06/30)
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- COMPOSITIONS AND METHODS FOR THE TREATMENT OF SEVERE PAIN
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The invention relates to the compounds of formula I or its pharmaceutical acceptable salts, as well as polymorphs, solvates, enantiomers, stereoisomers and hydrates thereof. The pharmaceutical compositions comprising an effective amount of compounds of formula I, and methods for the treatment of severe pain may be formulated for oral, buccal, rectal, topical, transdermal, transmucosal, intravenous, parenteral administration, syrup, or injection. Such compositions may be used to treatment of chronic pain, generalized pain disorders, leukemia, cancer, chronic pain, chemotherapy induced pain, epilepsy, migraine, neuropathic pain, post herpetic neuralgia, neuralgia, pain, drug addiction, detoxification of drugs, Alzheimer's disease, multiple sclerosis, multiple sclerosis, restless legs syndrome (RLS), cluster headache, depression, fibromyalgia, amyotrophic lateral sclerosis (ALS), convulsions, partial seizures, mood-stabilizing agent and bipolar disorder.
- -
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Paragraph 0122; 0123; 0124
(2015/06/10)
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- Direct transformation of primary nitro compounds into nitriles with sodium-dithionite
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A new and practical direct transformation of primary nitro compounds into nitriles with sodium dithionite is described. The reaction is simple, convenient and eliminates the use of expensive and moisture-sensitive reagents. Georg Thieme Verlag Stuttgart New York.
- Temelli, Baris,Unaleroglu, Canan
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p. 1407 - 1412
(2014/06/09)
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- Metal-free, one-pot oxidative conversion of aldehydes to primary thioamides in aqueous media
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One-pot tandem reactions of a variety of aldehydes with aqueous ammonia, molecular iodine, and O,O-diethyl dithiophosphoric acid readily afford the corresponding primary thioamides. This is an inexpensive, practical, and metal-free way of accessing various thioamides from aldehydes in aqueous media. The pure products are obtained simply by filtration followed by successive washing with aqueous sodium thiosulfate and water. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.]
- Yadav, Arvind K.,Srivastava, Vishnu P.,Yadav, Lal Dhar S.
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supporting information
p. 408 - 416
(2014/01/06)
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- Zinc-catalyzed direct cyanation of indoles and pyrroles: Nitromethane as a source of a cyano group
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With nitromethane and diphenylsilane (Ph2SiH2), zinc triflate behaves as a Lewis acid catalyst for the cyanation of nitrogen-containing heteroarenes such as indoles and pyrroles. This is the first realization of the Lewis acid-catalyzed direct cyanation of a C(aryl)-H bond with no CN group-containing cyanating agent.
- Nagase, Yuta,Sugiyama, Tetsuya,Nomiyama, Shota,Yonekura, Kyohei,Tsuchimoto, Teruhisa
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p. 347 - 352
(2014/05/20)
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- Chemoselective and direct functionalization of methyl benzyl ethers and unsymmetrical dibenzyl ethers by using iron trichloride
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Methyl and benzyl ethers are widely utilized as protected alcohols due to their chemical stability, such as the low reactivity of the methoxy and benzyloxy groups as leaving groups under nucleophilic conditions. We have established the direct azidation of chemically stable methyl and benzyl ethers derived from secondary and tertiary benzyl alcohols. The present azidation chemoselectively proceeds at the secondary or tertiary benzylic positions of methyl benzyl ethers or unsymmetrical dibenzyl ethers and is also applicable to direct allylation, alkynylation, and cyanation reactions, as well as the azidation. The present methodologies provide not only a novel chemoselectivity but also the advantage of shortened synthetic steps, due to the direct process without the deprotection of the methyl and benzyl ethers. Ethers exchanged: Methyl and benzyl ethers are chemically stable and generally tolerant under nucleophilic substitution conditions. Iron-catalyzed direct functionalizations (e.g., azidation, allylation, alkynylation, and cyanation) of methyl and benzyl ethers derived from secondary and tertiary benzyl alcohols were established with excellent regioselectivities (see scheme; PG: protecting group; Bn: benzyl; Nu: nucleophile; TMS: trimethylsilyl). Copyright
- Sawama, Yoshinari,Goto, Ryota,Nagata, Saori,Shishido, Yuko,Monguchi, Yasunari,Sajiki, Hironao
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supporting information
p. 2631 - 2636
(2014/03/21)
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- Synergistic effect of a bis(proazaphosphatrane) in mild palladium-catalyzed direct α-arylations of nitriles with aryl chlorides
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The effect of a bis(proazaphosphatrane) ligand on the palladium-catalyzed direct α-arylation of nitriles with various aryl chlorides under mild conditions is reported. Comparisons of the catalytic properties of this ligand with those of three related mono(proazaphosphatrane)s under the same reaction conditions revealed that bis(proazaphosphatrane) displayed a synergistically enhanced activity. In the presence of the bis(proazaphosphatrane) ligand, ethyl cyanoacetate and primary as well as secondary nitriles were efficiently coupled with a wide variety of aryl chlorides that contained electron-rich, electron-poor, and electron-neutral groups.
- Han Kim, So,Jang, Wonseok,Kim, Min,Verkade, John G.,Kim, Youngjo
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p. 6025 - 6029
(2015/03/30)
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- Regio- and enantioselective aminofluorination of alkenes
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Enantio- and regioselective: The intramolecular enantioselective aminofluorination of unactivated olefins was achieved by using a chiral iodo(III) difluoride salt. A highly regioselective aminofluorination of styrenes to access 2-fluoro-2-phenylethanamines was also developed. Copyright
- Kong, Wangqing,Feige, Pascal,De Haro, Teresa,Nevado, Cristina
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supporting information
p. 2469 - 2473
(2013/03/29)
-
- COMPOSITIONS AND METHODS FOR THE TREATMENT OF SEVERE PAIN
-
The invention relates to the compounds of formula (I) or its pharmaceutical acceptable salts, as well as polymorphs, solvates, enantiomers, stereoisomers and hydrates thereof. The pharmaceutical compositions comprising an effective amount of compounds of formula (I), and methods for the treatment of severe pain may be formulated for oral, buccal, rectal, topical, transdermal, transmucosal, intravenous, parenteral administration, syrup, or injection. Such compositions may be used to treatment of chronic pain, generalized pain disorders, leukemia, cancer, chronic pain, chemotherapy induced pain, epilepsy, migraine, neuropathic pain, post herpetic neuralgia, neuralgia, pain, drug addiction, detoxification of drugs, Alzheimer's disease, multiple sclerosis, multiple sclerosis restless legs syndrome (RLS), cluster headache, depression, fibromyalgia, amyotrophic lateral sclerosis (ALS), convulsions, partial seizures, mood-stabilizing agent and bipolar disorder.
- -
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Paragraph 00102
(2013/12/03)
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- Process development and optimization for production of a potassium ion channel blocker, ICA-17043
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A scalable process for the manufacture of a potassium ion channel blocker was developed and optimized. Key features of the process include an optimized Grignard reaction, a direct cyanation of the intermediate trityl alcohol derivative, and an improved nitrile hydrolysis protocol, relative to the original acidic hydrolysis conditions, to generate the crude active pharmaceutical ingredient (API) with >95% HPLC purity. The Grignard and the cyanation reactions could be telescoped, resulting in an improved throughput compared to the original four-step process. An effective recrystallization of the API was also developed and the process scaled up to manufacture multiple batches at the pilot scale.
- Mobele, Bingidimi I.,Venkatraman, Sripathy,McNaughton-Smith, Grant,Gibb, Cameron,Ulysse, Luckner G.,Lindmark, Carl A.,Shaw, Stephen,Marron, Brian,Spear, Kerry,Suto, Mark J.
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p. 1385 - 1392
(2012/11/07)
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- Electrochemical oxidation of amides of type Ph2CHCONHAr
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Anodic oxidation of N-aryl-2,2-diphenylacetamides in acetonitrile undergoes three types of bond-cleavage, one between the benzylic carbon and the carbonyl group, the second between a carbonyl and 'N', and the third between the 'N' atom and aryl group. The selectivity of the cleavage and nature of emerged products is highly dependent on the nature of substituent attached to the aryl group. For example, electron-withdrawing groups direct the benzyl-carbonyl bond-breaking whereas electron-donating substituents favor the N-aryl bond cleavage. The type of products obtained involve benzophenone, 2,2-diphenylacetamide, N-(diphenylmethylene)acetamide, N-(diphenylmethyl)acetamide, α-lactam (1-acetyl-3,3-diphenylaziridin-2-one, as a 1:1 complex with 2,4-dinitroaniline) and aniline derivatives.
- Golub, Tatiana,Becker, James Y.
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experimental part
p. 3906 - 3912
(2012/06/04)
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- Zn(OTf)2 - Catalyzed direct cyanation of benzylic alcohols - A novel synthesis of α-aryl nitriles
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This work demonstrates an efficient method to prepare α-aryl nitriles by direct cyanation of benzylic alcohol with TMSCN in the presence of a catalytic amount of Zn(OTf)2 under heating condition. A variety of benzylic alcohols can be converted into the corresponding α-aryl nitriles in good to excellent yields. 2012 Elsevier Ltd. All rights reserved.
- Theerthagiri, Palani,Lalitha, Appaswami
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supporting information
p. 5535 - 5538
(2012/11/07)
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- Synthesis of α-Aryl nitriles through palladium-catalyzed decarboxylative coupling of cyanoacetate salts with aryl halides and triflates
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Worth its salt: The palladium-catalyzed decarboxylative coupling of the cyanoacetate salt as well as its mono- and disubstituted derivatives with aryl chlorides, bromides, and triflates is described (see scheme). This reaction is potentially useful for the preparation of a diverse array of α-aryl nitriles and has good functional group tolerance. S-Phos=2-(2,6- dimethoxybiphenyl)dicyclohexylphosphine), Xant-Phos=4,5-bis(diphenylphosphino)- 9,9-dimethylxanthene. Copyright
- Shang, Rui,Ji, Dong-Sheng,Chu, Ling,Fu, Yao,Liu, Lei
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supporting information; experimental part
p. 4470 - 4474
(2011/06/24)
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- Fe(OTf)3-catalyzed reaction of benzylic acetates with organosilicon compounds
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Fe(OTf)3-catalyzed reaction of benzylic acetates with allyltrimethylsilane, azidotrimethylsilane, and cyanotrimethylsilane afforded the corresponding allylated, azido, and cyano products in high yields. 2-Trimethylsilyl-substituted benzofuran and indole worked well to furnish the benzyl-substituted benzofuran and indoles. Georg Thieme Verlag Stuttgart New York.
- Chan, Li Yan,Kim, Sundae,Chung, Wan Ting,Long, Chong,Kim, Sunggak
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experimental part
p. 415 - 419
(2011/04/22)
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- Straightforward conversion of alcohols into nitriles
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The reaction of various alcohols with cyanogen bromide, triphenylphosphine, and a base afforded the corresponding nitrile in satisfactory yields. Copyright
- Tarrade-Matha, Aurelie,Pillon, Florence,Doris, Eric
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experimental part
p. 1646 - 1649
(2010/07/09)
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- Synthesis of α-aryl nitriles through B(C6F5)3-catalyzed direct cyanation of α-aryl alcohols and thiols
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Various α-aryl nitriles have been prepared in excellent yield from the corresponding α-aryl alcohols employing 3 mol % of B(C6F5)3 (1) as Lewis acid catalyst and (CH3)3SiCN (TMSCN) as cyanide source. Cyano transfer from TMSCN to alcohol proceeds within short reaction time at rt. α-Aryl thiols also produce corresponding nitriles in good to excellent yield at reflux condition.
- Rajagopal, Gurusamy,Kim, Sung Soo
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experimental part
p. 4351 - 4355
(2009/09/30)
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- Palladium-catalyzed benzylic direct arylation of benzyl sulfones with aryl halides
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An effective palladium catalyst system for the direct arylation of benzyl sulfones with aryl halides has been developed. The catalytic reaction provides a facile route to diarylmethyl sulfones. The products can be transformed further via desulfonylative functionalization mediated by aluminum compounds.
- Niwa, Takashi,Yorimitsu, Hideki,Oshima, Koichiro
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experimental part
p. 1971 - 1976
(2009/08/07)
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- Controlled conversion of phenylacetic acids to phenylacetonitriles or benzonitriles using bis(2-methoxyethyl)aminosulfur trifluoride
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A mild, efficient, and practical method for the one-step synthesis of benzonitriles from phenylacetic acids using bis(2-methoxyethyl)aminosulfur trifluoride is described. The reaction was easily extended to the synthesis of the corresponding phenylacetonitriles by inclusion of triethylphosphine.
- Kangani, Cyrous O.,Day, Billy W.,Kelley, David E.
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p. 914 - 918
(2008/09/17)
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- Synthesis of alkyl iodides/nitriles from carbonyl compounds using novel ruthenium tris(2,2,6,6-tetramethyl-3,5-heptanedionate) as catalyst
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Aldehydes and ketones were hydrogenated to the corresponding alcohols, which were then transformed in situ into their respective iodides and nitriles in good yields. A structurally well-defined O-containing transition metal complex, Ru (TMHD)3, was found to be the active catalyst for hydrogenation, iodination and cyanation reactions. It has high affinity for the transformation of benzylic alcohols to iodides and nitriles.
- Bhor, Malhari D.,Panda, Anil G.,Nandurkar, Nitin S.,Bhanage, Bhalchandra M.
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body text
p. 6475 - 6479
(2009/04/06)
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- Direct, facile synthesis of acyl azides and nitriles from carboxylic acids using bis(2-methoxyethyl)aminosulfur trifluoride
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A mild, efficient, and practical method for the one-step synthesis of acyl azides from carboxylic acids using bis(2-methoxyethyl)aminosulfur trifluoride is described. The reaction was easily extended to the synthesis of the corresponding nitriles by the inclusion of phosphorous reagents. The method can be applied to the synthesis of optically active nitriles in high yields, and is compatible with fluorous phosphines.
- Kangani, Cyrous O.,Day, Billy W.,Kelley, David E.
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p. 5933 - 5937
(2008/02/10)
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- Straightforward construction of diarylmethane skeletons via aryne insertion into carbon-carbon σ-bonds
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Two molar amounts of arynes were found to couple with nitriles via carbon-carbon σ-bond cleavage, assembling diverse diarylmethane skeletons in a straightforward manner. The Royal Society of Chemistry.
- Yoshida, Hiroto,Watanabe, Masahiko,Morishita, Takami,Ohshita, Joji,Kunai, Atsutaka
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p. 1505 - 1507
(2008/02/02)
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- A simple one-pot procedure for the direct conversion of alcohols into alkyl nitriles using TsIm
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A convenient and efficient one-pot preparation of nitriles from alcohols using N-(p-toluenesulfonyl)imidazole (TsIm) is described. In this method, treatment of alcohols with a mixture of NaCN, TsIm and triethylamine in the presence of catalytic amounts of tetra-n-butylammonium iodide (TBAI) in refluxing DMF furnishes the corresponding alkyl nitriles in good yields. This methodology is highly efficient for various structurally diverse alcohols with selectivity for ROH: 1° > 2° > 3°.
- Soltani Rad, Mohammad Navid,Khalafi-Nezhad, Ali,Behrouz, Somayeh,Faghihi, Mohammad Ali
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p. 6779 - 6784
(2008/02/13)
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- Iridium-catalyzed selective C-C bond cleavage of nitriles and ketones
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Selective and catalytic C-C bond cleavage of pentanedinitriles and 5-oxohexanenitriles can be performed in the presence of iridium hydride complex IrH5(Pi-Pr3)2 (1). The key steps of this reaction are α-C-H activation of t
- Terai, Hiroki,Takaya, Hikaru,Murahashi, Shun-Ichi
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p. 2185 - 2187
(2007/10/03)
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- Efficient conversion of tetrahydropyranyl (THP) ethers to their corresponding cyanides with triphenylphosphine/2,3-dichloro-5,6- dicyanobenzoquinone/n-Bu4 NCN
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Tetrahydropyranyl ethers were converted to their corresponding alkyl cyanides efficiently by using the triphenylphosphine/ 2,3-dichloro-5,6- dicyanobenoquinone / n-Bu4 NCN system in refluxing acetonitrile with good-to-excellent yields.
- Akhlaghinia, Batool
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p. 1783 - 1786
(2007/10/03)
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- Conversion of Alcohols, Thiols, and Trimethysilyl Ethers to Alkyl Cyanides Using Triphenylphosphine/2,3-Dichlorol-5,6-dicyanobenzoquinone/n-Bu 4NCN
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Triphenylphosphine and 2,3-dichloro-5,6-dicyanobenzoquinone afford an adduct, which in the presence of n-Bu4NCN converts alcohols, thiols, and trimethylsilyl ethers into their corresponding alkyl cyanides in good to excellent yields at room tem
- Iranpoor, Nasser,Firouzabadi, Habib,Akhlaghinia, Batool,Nowrouzi, Najmeh
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p. 2562 - 2564
(2007/10/03)
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- P(i-BuNCH2CH2)3N: An efficient ligand for the direct α-arylation of nitriles with aryl bromides
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A new catalyst system for the synthesis of α-aryl-substituted nitriles is reported. The bicyclic triaminophosphine P(i-BuNCH 2CH2)3N (1b) serves as an efficient and versatile ligand for the palladium-catalyzed direct α-arylation of nitriles with aryl bromides. Using ligand 1b, ethyl cyanoacetate and primary as well as secondary nitriles are efficiently coupled with a wide variety of aryl bromides possessing electron-rich, electron-poor, electron-neutral, and sterically hindered groups.
- You, Jingsong,Verkade, John G.
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p. 8003 - 8007
(2007/10/03)
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- Cascade Transformations of (2,2-Diaryl-3,3-dichloroaziridin-1-yl)acetates
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Esters of (2,2-diaryl-3,3-dichloroaziridin-1-yl)acetic acid prepared from glycine derivatives under alkylation conditions afford esters of 2-[N-alkyl-N-(2,2-diaryl-1-cyanovinyl)amino]-3,3-diarylacrylic acid in 20-40% yield. The reaction resulting in these compounds proceeds through a cascade of 3-chloro-2-azadiene and ylide intermediates. 3-Chloro-2-azadienes originating from (2,2-diaryl-3,3-dichloroaziridin-1-yl)-acetates react with primary and secondary amines at the carbon atom of imine group providing ketenimines which undergo ketenimine-nitrile rearrangement or fragmentation. The other bases (KOH, MeONa, DBU) effect dehydrochlorination of the mentioned 3-chloro-2-azadienes giving nitrile-ylides which are trapped by nucleophilic reagents. The 3-chloro-2-azadiene obtained from methyl (2,2-diaryl-3,3-dichloroaziridin-1-yl)- acetate and DBU was relatively stable and was isolated as an individual compound. (2,2-diaryl-3,3-dichloroaziridin-1-yl)propionates behave as nonfunctionalized dichloroaziridines.
- Khlebnikov,Novikov,Kusei,Kopf,Kostikov
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p. 559 - 573
(2007/10/03)
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- A General Method for the Direct α-Arylation of Nitriles with Aryl Chlorides
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The long-standing challenge of developing a general method for the title methodology is met for a broad range of aryl chlorides through the use of bicyclic P(iBuNCH2CH2)3N (1) as a bulky electron-rich ligand for palladium (see scheme, dba = dibenzylideneacetone).
- You, Jingsong,Verkade, John G.
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p. 5051 - 5053
(2007/10/03)
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- The synthesis of alkyl aryl nitriles from N-(1-arylalkylidene)-cyanomethylamines. Part 2. Mechanism
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The mechanism of the rearrangement of N-(1-arylalkylidene)cyanomethylamines ArC(=NCH2CN)R 1 to the corresponding nitriles ArCH(CN)R2 (in DMF, at 150°C, with K2CO3) is described. Reaction 1 → 2 was investigated for different types of imine 1, and it was found that with a leaving group other than CN- the reaction does not proceed to yield the nitrile, whereas imines such as PhC(=NCH2CN)H, prepared starting from aldehydes rather than ketones, yield the expected phenylacetonitrile even at temperatures as low as 120°C. Evidence for the mechanism comes from a study of the reactivity of the postulated intermediates: 2-cyano-3-phenylaziridine 4c, and 2,2-diphenyl-2H-azirine 5b. The route involving aziridine 4c is ruled out, since this compound does not react at all under the investigated conditions. The 2H-azirine 5b instead, yields the corresponding diphenylacetonitrile in DMF with K2CO3, at 150°C. The transformation seems to involve an initial deprotonation, followed by an intramolecular ring closure-CN elimination step, which yields the 2H-azirine. The azirine then isomerizes to the nitrile. Additional evidence for the intermediacy of the 2H-azirine, based on 1H NMR monitoring of the reaction 1 → 2, is described. Finally, the results of a simple isotope exchange experiment provide a rationale for the previously observed scrambling of labels, and further confirm the proposed mechanism.
- Perosa, Alvise,Selva, Maurizio,Tundo, Pietro
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p. 1033 - 1037
(2007/10/03)
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- Synthesis, characterization, and reactivity of arylpalladium cyanoalkyl complexes: Selection of catalysts for the α-arylation of nitriles
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A new coupling process, the palladium-catalyzed α-arylation of nitriles, was developed by exploring the structure and reactivity of arylpalladium cyanoalkyl complexes. Complexes of 1,2-bis(diphenylphosphino)benzene (DPPBz), 1,1′-bis(di-i-propylphosphino)ferrocene (DiPrPF), racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP), and diphenylethylphosphine (PPh2Et) were prepared. Coordination to palladium through the α-carbon was observed for DPPBz-ligated complexes and for complexes of primary and benzylic nitrile anions. However, the anion of isobutyronitrile was coordinated to palladium through the cyano-nitrogen when the complex was ligated by DiPrPF. The isobutyronitrile anion displaced a phosphine ligand to form a C,N-bridged dimer when generated from PPh2Et-ligated palladium. These results suggest that the nitrile anion preferentially coordinates to palladium through the carbon atom in the absence of steric effects. Thermolysis of the arylpalladium cyanoalkyl complexes led to reductive elimination that formed α-aryl nitriles. The high yields and short reaction times observed for BINAP-ligated complexes suggested that BINAP-ligated palladium catalysts might be appropriate for the arylation of nitriles. Initial results on a palladium-catalyzed process for the direct coupling of aryl bromides and primary, benzylic, and secondary nitrile anions to form α-aryl nitriles in good yields are reported. Copyright
- Culkin, Darcy A.,Hartwig, John F.
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p. 9330 - 9331
(2007/10/03)
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- A direct and efficient synthetic method for nitriles from ketones
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Cyclic cyano derivatives 3 were obtained by the reaction of Me3SiCN / ZnI2 with the cyclic ketones 2 which gave the trimethylsilyloxy nitriles 4. They were directly transformed to cyano derivatives 3 (70-80% yield) by the reductive reagent Me3SiCl-NaI in acetonitrile in the presence of H2O.
- Kloubert, Stephane,Mathe-Allainmat, Monique,Andrieux, Jean,Langlois, Michel
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p. 2873 - 2887
(2007/10/03)
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- Histamine H1 receptor ligands - Part II. Synthesis and in vitro pharmacology of 2-[2-(phenylamino)thiazol-4-yl]ethanamine and 2-(2-benzhydrylthiazol-4-yl)ethanamine derivatives
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New 2-[2-(phenylamino)thiazol-4-yl]ethanamine and 2-(2-benzhydrylthiazol-4-yl)ethanamine derivatives were prepared and tested in vitro as H1 receptor antagonists. The compounds with 2-phenylamino substitution with meta-halide substituents at the phenyl ring, showed weak H1-antagonistic activity (pA2: 4.62-5.04) and this activity was completely lost in the case of meta-methyl substituent (pA2 : 4). When the phenylamino group was replaced by benzhydryl groups of classic antihistamines, the resulting compounds exhibited slightly improved H1-antagonistic activity (at the meta-position pA2: 6.38-6.15; at the para-position pA2: 6.04-5.87).
- Walczynski, Krzysztof,Guryn, Roman,Zuiderveld, Obbe P.,Zhang, Ming-Qiang,Timmerman, Henk
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p. 569 - 574
(2007/10/03)
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