cas 56578-35-9, 2-PROPENAL, 3-(4-METHYLPHENYL)-,(2E)

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An efficient Pd@Pro-GO heterogeneous catalyst for the α, β-dehydrogenation of saturated aldehyde and ketones
An Efficient Pd@Pro-GO heterogeneous catalyst was developed that can promote the α, β-dehydrogenation of saturated aldehyde and ketones in the yield of 73% ? 92% at mild conditions without extra oxidants and additives. Pd@Pro-GO heterogeneous catalyst was synthesized via two steps: firstly, the Pro-GO was obtained by the esterification reaction between graphene oxide (GO) and N-(tert-Butoxycarbonyl)-L-proline (Boc-Pro-OH), followed by removing the protection group tert-Butoxycarbonyl (Boc), which endowed the proline-functionalized GO with both the lewis acid site (COOH) and the bronsted base site (NH), besides, the pyrrolidine of proline also can form imine with aldehydes to activate these substrates; Second, palladium was dispersed on the proline-functionalized GO (Pro-GO) to obtained heterogeneous catalyst Pd@Pro-GO. Mechanistic studies have shown that the Pd@Pro-GO-catalyzed α,β-dehydrogenation of saturated aldehyde and ketones was realized by an improved heterogeneously catalyzed Saegusa oxidation reaction. Based on the obove characteristics, the Pd@Pro-GO will be widely used in the transition metal catalytic field.
Pan, Gao-Fei,Wang, Zhe,Chang, Yi-Yuan,Hao, Yue,Wang, Yi-Chen,Xing, Rui-Guang
supporting information

(2021/12/30)

Tandem oxidation-dehydrogenation of (hetero)arylated primary alcohols via perruthenate catalysis
Tandem oxidative-dehydrogenation of primary alcohols to give a,b-unsaturated aldehydes in one pot are rare transformations in organic synthesis, with only two methods currently available. Reported herein is a novel method using the bench-stable salt methyltriphenylphosphonium perruthenate (MTP3), and a new co-oxidant NEMO&middoPF6 (NEMO = N-ethyl-N-hydroxymorpholinium) which provides unsaturated aldehydes in low to moderate yields. The Ley-Griffith oxidation of (hetero)arylated primary alcohols with N-oxide co-oxidants NMO (NMO = N-methylmorpholine N-oxide)/NEMO, is expanded by addition of the N-oxide salt NEMO&middoPF6 to convert the intermediate saturated aldehyde into its unsaturated counterpart. The discovery, method development, reaction scope, and associated challenges of this method are highlighted. The conceptual value of late-stage dehydrogenation in natural product synthesis is demonstrated via the synthesis of a polyene scaffold related to auxarconjugatin B.
Bettencourt, Christian J.,Chow, Sharon,Moore, Peter W.,Read, Christopher D.G.,Jiao, Yanxiao,Bakker, Jan Peter,Zhao, Sheng,Bernhardt, Paul V.,Williams, Craig M.
p. 652 - 659
(2021/09/08)

Selective Rhodium-Catalyzed Hydroformylation of Terminal Arylalkynes and Conjugated Enynes to (Poly)enals Enabled by a π-Acceptor Biphosphoramidite Ligand
The hydroformylation of terminal arylalkynes and enynes offers a straightforward synthetic route to the valuable (poly)enals. However, the hydroformylation of terminal alkynes has remained a long-standing challenge. Herein, an efficient and selective Rh-catalyzed hydroformylation of terminal arylalkynes and conjugated enynes has been achieved by using a new stable biphosphoramidite ligand with strong π-acceptor capacity, which affords various important E-(poly)enals in good yields with excellent chemo- and regioselectivity at low temperatures and low syngas pressures.
Zhao, Jiangui,Zheng, Xueli,Tao, Shaokun,Zhu, Yuxin,Yi, Jiwei,Tang, Songbai,Li, Ruixiang,Chen, Hua,Fu, Haiyan,Yuan, Maolin
supporting information
p. 6067 - 6072
(2021/08/16)

Iron-Catalyzed ?±,?-Dehydrogenation of Carbonyl Compounds
An iron-catalyzed α,β-dehydrogenation of carbonyl compounds was developed. A broad spectrum of carbonyls or analogues, such as aldehyde, ketone, lactone, lactam, amine, and alcohol, could be converted to their α,β-unsaturated counterparts in a simple one-step reaction with high yields.
Zhang, Xiao-Wei,Jiang, Guo-Qing,Lei, Shu-Hui,Shan, Xiang-Huan,Qu, Jian-Ping,Kang, Yan-Biao
supporting information
p. 1611 - 1615
(2021/03/03)

Substrate-Controlled Chemo-/Enantioselective Synthesis of α-Benzylated Enals and Chiral Cyclopropane-Fused 2-Chromanone Derivatives
Substrate-controlled cascade reactions between α,β-unsaturated aldehydes or their analogues and 2,4-dinitrobenzyl chloride in the presence of a chiral secondary amine as the catalyst and base were developed, to obtain a broad spectrum of α-benzylated enals and enantioenriched cyclopropane-fused chroman-2-one derivatives. The cyclopropane-tethered iminium ion clearly served as a key intermediate in these reactions to trigger stereochemical outcomes, one of which was supported by a control experiment. (Figure presented.).
Byeon, Huimyoung,Ryu, Sunghyeon,Yoo, Eun Jeong,Yang, Jung Woon
supporting information
p. 5085 - 5091
(2021/09/20)

Potent Inhibition of Nicotinamide N-Methyltransferase by Alkene-Linked Bisubstrate Mimics Bearing Electron Deficient Aromatics
Nicotinamide N-methyltransferase (NNMT) methylates nicotinamide (vitamin B3) to generate 1-methylnicotinamide (MNA). NNMT overexpression has been linked to a variety of diseases, most prominently human cancers, indicating its potential as a therapeutic target. The development of small-molecule NNMT inhibitors has gained interest in recent years, with the most potent inhibitors sharing structural features based on elements of the nicotinamide substrate and the S-adenosyl-l-methionine (SAM) cofactor. We here report the development of new bisubstrate inhibitors that include electron-deficient aromatic groups to mimic the nicotinamide moiety. In addition, a trans-alkene linker was found to be optimal for connecting the substrate and cofactor mimics in these inhibitors. The most potent NNMT inhibitor identified exhibits an IC50 value of 3.7 nM, placing it among the most active NNMT inhibitors reported to date. Complementary analytical techniques, modeling studies, and cell-based assays provide insights into the binding mode, affinity, and selectivity of these inhibitors.
Buijs, Ned,Campagna, Roberto,Emanuelli, Monica,Gao, Yongzhi,Innocenti, Paolo,Jespers, Willem,Martin, Nathaniel I.,Parsons, Richard B.,Sartini, Davide,Van Haren, Matthijs J.,Van Westen, Gerard J. P.,Zhang, Yurui,Gutiérrez-De-Terán, Hugo
p. 12938 - 12963
(2021/09/11)

Scalable Aerobic Oxidation of Alcohols Using Catalytic DDQ/HNO3
A selective, practical, and scalable aerobic oxidation of alcohols is described that uses catalytic amounts of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and HNO3, with molecular oxygen serving as the terminal oxidant. The method was successfully applied to the oxidation of a wide range of benzylic, propargylic, and allylic alcohols, including two natural products, namely, carveol and podophyllotoxin. The conditions are also applicable to the selective oxidative deprotection of p-methoxybenzyl ethers.
Arseniyadis, Stellios,Clavier, Louis,Copin, Chloé,Fournier, Jean,Giffard, Jean-Fran?ois,Jean, Alexandre,Katsina, Tania,Macedo Portela Da Silva, Nayane,Tamion, Rodolphe
supporting information
p. 856 - 860
(2020/07/14)

Amino acid derivative, feed composition and application thereof
The invention provides an amino acid derivative, a feed composition and application thereof, and belongs to the technical field of animal feed additives. The amino acid derivative is a compound with astructure shown as a formula (I), and a stereoisomer, a tautomer, a solvate, a metabolite, a feed acceptable salt or a prodrug thereof. In formula (I) shown in the specification, Z is a C1-C3 alkylene group. X is an indole ring group with a structure shown as a formula (II). The formula (II) is shown in the specification, wherein Y is phenyl with the structure shown in the formula (III) shown inthe specification. The amino acid derivative is used as an animal feed additive, and can promote the growth of animals and improve the feed conversion.
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Paragraph 0121-0123; 0126

(2020/05/14)

Palladium-Catalyzed [5 + 2] Annulation of Vinylethylene Carbonates with Barbiturate-Derived Alkenes
A palladium/XantPhos-catalyzed [5 + 2] annulation of VECs with electron-deficient alkenes having an isolated carbon-carbon double bond has been developed to afford spirobarbiturate-tetrahydrooxepines. This study provides an expedient assembly of biologically interesting spirobarbiturate-tetrahydrooxepines. The easy scalability and versatile transformability of the reaction products were also exhibited.
Chen, Yuehua,Deng, Hao,Gao, Xing,Guo, Hongchao,Jiang, Feng,Wang, Wei,Wu, Yongjun,Zhu, Dongyu
supporting information
p. 7158 - 7163
(2020/10/02)

Highly γ-Regioselective 1,2-Addition of α,β-Unsaturated Oxime Ethers with Allylzinc Bromides: A Straightforward Approach for the Synthesis of Homoallylic Amines
A highly regioselective reaction between allylzinc bromide reagents and α,β-unsaturated oxime ethers for the one-step synthesis of the homoallylic amines is reported. This process is a regioselective 1,2-addition reaction providing a new γ-position with carbon-carbon bond formation. Furthermore, the reaction substrates are widely applicable and can be produced in a high yield.
Yang, Bo,Zhang, Songlin
supporting information
p. 3736 - 3746
(2019/09/30)

Highly efficient and practical aerobic oxidation of alcohols by inorganic-ligand supported copper catalysis
The oxidation of alcohols to aldehydes or ketones is a highly relevant conversion for the pharmaceutical and fine-chemical industries, and for biomass conversion, and is commonly performed using stoichiometric amounts of highly hazardous oxidants. The aerobic oxidation of alcohols with transition metal complex catalysts previously required complicated organic ligands and/or nitroxyl radicals as co-catalysts. Herein, we report an efficient and eco-friendly method to promote the aerobic oxidation of alcohols using an inorganic-ligand supported copper catalyst 1, (NH4)4[CuMo6O18(OH)6], with O2 (1 atm) as the sole oxidant. Catalyst 1 is synthesized directly from cheap and commonly available (NH4)6Mo7O24·4H2O and CuSO4, which consists of a pure inorganic framework built from a central CuII core supported by six MoVIO6 inorganic scaffolds. The copper catalyst 1 exhibits excellent selectivity and activity towards a wide range of substrates in the catalytic oxidation of alcohols, and can avoid the use of toxic oxidants, nitroxyl radicals, and potentially air/moisture sensitive and complicated organic ligands that are not commercially available. Owing to its robust inorganic framework, catalyst 1 shows good stability and reusability, and the catalytic oxidation of alcohols with catalyst 1 could be readily scaled up to gram scale with little loss of catalytic activity, demonstrating great potential of the inorganic-ligand supported Cu catalysts in catalytic chemical transformations.
Wei, Zheyu,Ru, Shi,Zhao, Qixin,Yu, Han,Zhang, Gang,Wei, Yongge
supporting information
p. 4069 - 4075
(2019/08/07)

Samarium Iodide-Promoted Asymmetric Reformatsky Reaction of 3-(2-Haloacyl)-2-oxazolidinones with Enals
3-(2-Haloacyl)-2-oxazolidinones were shown to react with enals in an asymmetric SmI2-promoted Reformatsky reaction to give stereochemically well-defined 3-hydroxy-4-alkenyl- and 3-hydroxy-2-methyl-4-alkenyl imides. Chirality transfer of the Evans (S)-oxazolidinone unit via a Zimmerman-Traxler-like transition state resulted in Reformatsky products with a relative syn-configuration. The absolute configuration of compounds obtained is opposite to the corresponding products obtained via aldol addition of boron enolates to enals using the same Evans oxazolidinones.
Baro, Angelika,Dallavalle, Sabrina,Hasnik, Fabian,Laschat, Sabine,Sinast, Moritz,Sube, Tobias,Wischnat, Jonathan,Zuccolo, Marco
supporting information

(2019/08/26)

Iron(III)/O2-Mediated Regioselective Oxidative Cleavage of 1-Arylbutadienes to Cinnamaldehydes
A simple, efficient, and environmentally benevolent regioselective oxidative cleavage of 1-arylbutadienes to cinnamaldehydes mediated by iron(III) sulfate/O2 has been developed. The reaction offered good yields and excellent regioselectivity and showed good functional group tolerance (31 examples). The method is important, as few reports with limited substrate scope are available for such excellent oxidative cleavage of conjugated dienes.
Bhowmik, Amit,Fernandes, Rodney A.
supporting information
p. 9203 - 9207
(2019/11/14)

Lipase/Oxovanadium Co-Catalyzed Dynamic Kinetic Resolution of Propargyl Alcohols: Competition between Racemization and Rearrangement
Quantitative conversion of racemic propargyl alcohols into optically active propargyl esters with up to 99% ee has been achieved by lipase/oxovanadium co-catalyzed dynamic kinetic resolution, which combines the lipase-catalyzed enantioselective esterification of the racemic substrates and the in situ racemization of the remaining enantiomers. The success is owed to our discovery of a magic solvent, (trifluoromethyl)benzene, that accelerated the racemization while sufficiently suppressing the common oxovanadium-catalyzed rearrangement of propargyl alcohols to irreversibly produce enals.
Kawanishi, Shinji,Oki, Shinya,Kundu, Dhiman,Akai, Shuji
p. 2978 - 2982
(2019/03/26)

Phosphorous acid promoted isomerization of propargyl alcohols to α,β-unsaturated carbonyl compounds
A metal-free and two-phase protocol for the Meyer-Schuster isomerization of propargyl alcohols to the corresponding α,β-unsaturated carbonyl compounds has been achieved in the presence of stoichiometric phosphorous acid aqueous solution, which produces the desired products in high yields with excellent stereoselectivity. Compared with the traditional methods, the procedure features broad scope of the substrates, mild conditions, and easy separation, providing an appealing alternative to the Meyer-Schuster reaction.
Gan, Xiaotang,Fu, Zuqi,Liu,Yan, Yani,Chen, Chao,Zhou, Yongbo,Dong, Jianyu
(2019/07/12)

Palladium-Catalyzed Formylation of Alkenylzinc Reagents with S-(4-Nitrophenyl) Thioformate
We report the synthesis of enal compounds by palladium-catalyzed formylation of alkenylzinc reagents with S-(4-nitrophenyl) thioformate. Various functional groups were tolerated in the present reaction. 1H NMR experiments revealed that the products had a non-protected formyl group, which can be utilized for further C–C bond formation reactions. We successfully achieved the one-pot synthesis of a 1,5-diene-3-ol compound via sequential formylation and allylation.
Haraguchi, Ryosuke,Tanazawa, Sho-Go,Tokunaga, Naoya,Fukuzawa, Shin-Ichi
p. 1761 - 1764
(2018/04/27)

Discovery of novel piperonyl derivatives as diapophytoene desaturase inhibitors for the treatment of methicillin-, vancomycin- and linezolid-resistant Staphylococcus aureus infections
Inhibition of S. aureus diapophytoene desaturase (CrtN) could serve as an alternative approach for addressing the tricky antibiotic resistance by blocking the biosynthesis of carotenoid pigment which shields the bacterium from host oxidant killing. In this study, we designed and synthesized 44 derivatives with piperonyl scaffold targeting CrtN and the structure-activity relationships (SARs) were examined extensively to bring out the discovery of 21b with potent efficacy and better hERG safety profile compared to the first class CrtN inhibitor benzocycloalkane derivative 2. Except the excellent pigment inhibitory activity against wild-type S. aureus, 21b also showed excellent pigment inhibition against four pigmented MRSA strains. In addition, H2O2 killing and human whole blood killing assays proved 21b could sensitize S. aureus to be killed under oxidative stress conditions. Notably, the murine study in vivo validated the efficacy of 21b against pigmented S. aureus Newman, vancomycin-intermediate S. aureus Mu50 and linezolid-resistant S. aureus NRS271.
Wei, Hanwen,Mao, Fei,Ni, Shuaishuai,Chen, Feifei,Li, Baoli,Qiu, Xiaoxia,Hu, Linghao,Wang, Manjiong,Zheng, Xinyu,Zhu, Jin,Lan, Lefu,Li, Jian
p. 235 - 251
(2018/01/17)

Gold catalyzed Heck-coupling of arenediazonium o-benzenedisulfonimides
Diazonium salts, and precisely arenediazonium o-benzenedisulfonimides, have been used for the first time as efficient electrophilic partners in gold catalyzed Heck-coupling reactions. The synthetic protocol was general, easy and gave the target products in satisfactory yields. Mechanistic insights revealed the fundamental roles of the o-benzenedisulfonimide anion as an electron transfer agent thath promotes a radical pathway that does not require the presence of photocatalysts or external oxidants.
Barbero, Margherita,Dughera, Stefano
p. 295 - 301
(2018/01/12)

Synthesis of Enones and Enals via Dehydrogenation of Saturated Ketones and Aldehydes
A general, efficient and economic palladium-catalyzed dehydrogenation to form enones or enals has been developed. The approach possesses extremely broad substrate scope including various linear or cyclic saturated ketones and aldehydes. The protocol is ligand-free, and molecular oxygen is used as the sole clean oxidant in the reaction. Due to mild reaction conditions, good functional group compatibility, and versatile utilities of enones and enals, the method can be applied in the late-stage synthesis of natural products, pharmaceuticals and fine chemicals. (Figure presented.).
Pan, Gao-Fei,Zhu, Xue-Qing,Guo, Rui-Li,Gao, Ya-Ru,Wang, Yong-Qiang
p. 4774 - 4783
(2018/11/10)

Palladium-catalyzed hydroformylation of terminal arylacetylenes with glyoxylic acid
A simple, practical and governable palladium-catalyzed hydroformylation of terminal arylacetylenes has been disclosed. The reaction proceeds under syngas-free conditions, using readily available glyoxylic acid as the formyl source, under mild conditions, giving rise to a broad range of α,β-unsaturated aldehydes.
Liu, Yang,Cai, Liangzhen,Xu, Sheng,Pu, Weiwen,Tao, Xiaochun
supporting information
p. 2166 - 2168
(2018/03/06)

Modular synthesis of (E)-cinnamaldehydes directly from allylarenes via a metal-free DDQ-mediated oxidative process
An efficient synthesis of (E)-cinnamaldehydes by a metal-free DDQ-mediated oxidative transformation of allylarenes was developed. The protocol provides a practical method to prepare diverse (E)-cinnamaldehydes with broad functional group tolerance in good to excellent yields, including easy access to natural products randainal and geranyloxy sinapyl aldehyde from plant extracts. Finally, the mechanism of a single-electron transfer process was proposed.
Xu, Ting-Ting,Jiang, Tao-Shan,Han, Xiao-Lan,Xu, Yuan-Hong,Qiao, Jin-Ping
p. 5350 - 5358
(2018/08/03)

Palladium-Catalyzed Regioselective Aerobic Allylic C?H Oxygenation: Direct Synthesis of α,β-Unsaturated Aldehydes and Allylic Alcohols
A protocol for the synthesis of α,β-unsaturated aldehydes and allylic alcohols from simple allylic hydrocarbons with water via palladium-catalyzed functionalization of allylic C?H bonds was described. Molecular oxygen is utilized as the sole oxidant in this oxygenation of terminal alkenes. This protocol features good functional group compatibility, broad substrate scope, and high atom- and step-economy. Moreover, the synthetic utility of this method can be highlighted by its application to the synthesis of ibuprofen, which is a highly potent analgesic. (Figure presented.).
Li, Chunsheng,Chen, Huoji,Li, Jianxiao,Li, Meng,Liao, Jianhua,Wu, Wanqing,Jiang, Huanfeng
supporting information
p. 1600 - 1604
(2018/03/05)

Hendrickson reagent induced rearrangement of aryl propargyl alcohols to α,β-unsaturated aldehydes
The Hendrickson reagent (triphenylphosphonium anhydride trifluoromethanesulfonate), prepared from the reaction of triphenylphosphine oxide (Ph3PO) and triflic anhydride (Tf2O) (2:1 stoichiometry), promotes dehydrations and various coupling reactions. The reagent has been used to transform oximes to nitriles and to prepare esters, amides and many other functional groups through the intermediacy of an alkoxyphosphonium salt. The reagent proved useful in heterocycle synthesis of thiazolines, imidazolines, quinoline precursors, isoquinolines, β-carbolines, phenanthridines, 11H-indolo[3,2-c]quinolines, quinoline-lactones, furoquinolinones, and indolizino[1,2-b]quinolin-9(11H)-ones. Moreover, the reagent has been key to the successful total synthesis of several natural products. Aryl propargyl alcohols with a terminal α-acetylenic group undergo rapid conversion to the corresponding α,β-unsaturated aldehydes at room temperature in dichloromethane in the presence of one equivalent of triphenylphosphonium anhydride trifluoromethanesulfonate. The reaction involved adding freshly distilled Tf2O (1.0 mmol) to a solution of Ph3PO (2.0 mmol) in CH2Cl2 (10 mL) at 0oC under N2 atmosphere. After stirring for 10 min, the propargyl alcohol (1.0 mmol) was added as a CH2Cl2 solution (2 mL), followed by the addition of water and Et3N (2.0 mmol) and further stirring at room temperature for 1h. Subsequent workup with 5% NaHCO3 (20 mL) and purification afforded α,β-unsaturated aldehydes. Eighteen aryl propargyl alcohol substrates with a terminal α-acetylenic group were transformed in good to excellent yields (71-85%) to enals. The methodology proved successful with secondary and tertiary alcohols with stereoselectivity favouring exclusively the E isomer. All the synthesized compounds are known and were characterized (1H,13C, and M.P) and compared to literature values. The method offers several advantages such as exclusive stereoselectivity, short reaction time, good yield, mild reaction conditions, and simple operational procedure.
Moussa, Ziad,Aljuhani, Ateyatallah
p. 845 - 853
(2018/11/06)

New Class of Anion-Accelerated Amino-Cope Rearrangements as Gateway to Diverse Chiral Structures
We report useful new lithium-assisted asymmetric anion-accelerated amino-Cope rearrangement cascades. A strategic nitrogen atom chiral auxiliary serves three critical roles, by (1) enabling in situ assembly of the chiral 3-amino-1,5-diene precursor, (2) facilitating the rearrangement via a lithium enolate chelate, and (3) imparting its influence on consecutive inter- or intramolecular C-C or C-X bond-forming events via resulting chiral enamide intermediates or imine products. The mechanism of the amino-Cope rearrangement was explored with density functional theory. A stepwise dissociation-recombination mechanism was found to be favored. The stereochemistry of the chiral auxiliary determines the stereochemistry of the Cope product by influencing the orientation of the lithium dienolate and sulfinylimine fragments in the recombination step. These robust asymmetric anion-accelerated amino-Cope enabled cascades open the door for rapid and predictable assembly of complex chiral acyclic and cyclic nitrogen-containing motifs in one pot.
Chogii, Isaac,Das, Pradipta,Fell, Jason S.,Scott, Kevin A.,Crawford, Mark N.,Houk,Njardarson, Jon T.
supporting information
p. 13141 - 13146
(2017/09/26)

Copper-catalyzed Mannich-type oxidative β-functionalization of tertiary amines
A copper-catalyzed Mannich-type oxidative β-functionalization reaction of amines has been developed. In the presence of an oxidant and a copper catalyst, tertiary amines reacted with N-tosylimines, providing synthetically important 1,3-diamines and enamines, respectively. Preliminary mechanistic studies suggested that the oxidation of the tertiary amine to the enamine intermediate triggers subsequent Mannich-type reactions with N-tosylimines and thus enables the direct β-functionalization of the tertiary amines.
Zhou, Min-Jie,Zhu, Shou-Fei,Zhou, Qi-Lin
supporting information
p. 8770 - 8773
(2017/08/09)

Expanding the scope of the Babler–Dauben oxidation: 1,3-oxidative transposition of secondary allylic alcohols
We report the catalytic chromium-mediated oxidation of secondary allylic alcohols to give α,β-unsaturated aldehydes with exclusive (E)-stereoselectivity. This facile procedure employs catalytic PCC (5?mol?%) and periodic acid (H5IO6) as a co-oxidant. This transformation occurs specifically with aromatic substituted allyl alcohols containing both electron withdrawing and electron donating substituents as well as a range of functional groups.
Killoran, Patrick M.,Rossington, Steven B.,Wilkinson, James A.,Hadfield, John A.
supporting information
p. 3954 - 3957
(2016/08/09)

Oxidative cleavage of allyl ethers by an oxoammonium salt
A method to oxidatively cleave allyl ethers to their corresponding aldehydes mediated by an oxoammonium salt is described. Using a biphasic solvent system and mild heating, cleavage proceeds readily, furnishing a variety of α,β-unsaturated aldehydes and ketones.
Kelly, Christopher B.,Ovian, John M.,Cywar, Robin M.,Gosselin, Taylor R.,Wiles, Rebecca J.,Leadbeater, Nicholas E.
p. 4255 - 4259
(2015/04/14)

Wittig Reactions of Trialkylphosphine-derived Ylides: New Directions and Applications in Organic Synthesis
The development of semi-stabilized, stabilized, and functionalized ylides derived from short-chain trialkylphosphines in the Wittig-type olefination reactions toward the synthesis of alkenes, including stilbenes, styrenes, and 1,3-dienes, as well as reagents for homologation reactions, are described. The methods allow easy access to alkenes with high (E)-stereoselectivity in good yield. These reactions are conducted with weak bases in aqueous media, which allows easy separation of water-soluble phosphine oxides. The development of a mild organocatalytic process for the Wittig reaction and extension toward the preparation of reporter stilbenes under biological conditions are also described. Applications toward the preparation of biologically active natural products and derivatives are discussed.
McNulty, James,McLeod, David,Das, Priyabrata,Zepeda-Velázquez, Carlos
p. 619 - 632
(2016/01/15)

A 2,6-bis(phenylamino)pyridinato titanium catalyst for the highly regioselective hydroaminoalkylation of styrenes and 1,3-butadienes
The C-C bond forming catalytic hydroaminoalkylation of terminal alkenes, 1,3-dienes, or styrenes allows a direct and highly atom efficient (100 %) synthesis of amines which can result in the formation of two regioisomers, the linear and the branched product. We present a new titanium catalyst with 2,6-bis(phenylamino)pyridinato ligands for intermolecular hydroaminoalkylation reactions of styrenes and 1-phenyl-1,3-butadienes that delivers the corresponding linear hydroaminoalkylation products with excellent regioselectivities. Linear progress: A new Ti complex with 2,6-bis(phenylamino) pyridinato ligands catalyzes highly regioselective hydroaminoalkylation reactions of styrenes. The process that directly gives access to the corresponding linear hydroaminoalkylation products offers a new and flexible synthetic approach towards pharmaceutically important 3-arylpropylamines. It is also possible to convert (E)-1-phenyl-1,3-butadienes into the corresponding linear products.
Doerfler, Jaika,Preuss, Till,Schischko, Alexandra,Schmidtmann, Marc,Doye, Sven
p. 7918 - 7922
(2014/08/05)

Synergistic catalysis: Enantioselective addition of Alkylbenzoxazoles to Enals
A novel catalytic enantioselective methodology based on synergistic catalysis is reported. The strategy involves: 1) the metal-Lewis-acid activation of alkylazaarenes, and 2) the secondary-amine activation of enals. Consequently, highly functionalized chiral alkylazaarenes were obtained in good yields and with reasonable stereoselectivity.
Meazza, Marta,Ceban, Victor,Pitak, Mateusz B.,Coles, Simon J.,Rios, Ramon
supporting information
p. 16853 - 16857
(2015/01/09)

Silicon-directed rhenium-catalyzed allylic carbaminations and oxidative fragmentations of γ-silyl allylic alcohols
A highly regioselective allylic substitution of β-silyl allylic alcohols has been achieved that provides the branched isomer as a single product. This high level of regiocontrol is achieved through the use of a vinyl silane group that can perform a Hiyama coupling providing 1,3-disubstituted allylic amines. An unusual oxidative fragmentation product was also observed at elevated temperature that appears to proceed by a Fleming-Tamao-type oxidation-elimination pathway.
Chavhan, Sanjay W.,Cook, Matthew J.
supporting information
p. 4891 - 4895
(2014/05/06)

Selective photoisomerization of methyl substituted nitro diphenylbutadienes
A series of p-nitro substituted trans-diphenylbutadienes is synthesized and their photophysical and photochemical properties are investigated. All the dienes have a very low quantum yield of fluorescence but exhibit remarkable solvatochromic emission shifts attributed to twisted intramolecular charge transfer. Photochemical irradiation of simple p-nitro substituted diphenylbutadienes reveals inefficient or no detectable photoisomerization. However, substituting a methyl group on the butadiene chain of p-nitro substituted diphenylbutadiene or replacing the nitro group with cyano group yields the corresponding trans-cis isomers. In the case of simple nitrodienes, strong intramolecular charge transfer character in the excited state aids dissipation of absorbed energy through non-photochemical and non-radiative channels. The steric effect caused by the presence of methyl group lowers the isomerization barrier in methyl substituted dienes leading to a regioselective isomerization.
Agnihotri, Harsha,Palakollu, Veerabhadra,Kanvah, Sriram
p. 40 - 49
(2014/11/12)

Br?nsted acid-catalyzed meyer-schuster rearrangement for the synthesis of α, β -unsaturated carbonyl compounds
An efficient and simple protocol for the Meyer-Schuster rearrangement of propargyl alcohols into α,β-unsaturated carbonyl compounds has been developed using catalytic amounts of p-toluenesulfonic acid in 1,2-dichloroethane.
Park, Jungmin,Yun, Jihee,Kim, Jaehyun,Jang, Dong-Jin,Park, Cheol Ho,Lee, Kooyeon
p. 1924 - 1929
(2014/07/07)

Titanium-catalyzed intermolecular hydroaminoalkylation of conjugated dienes
Ti me kangaroo down: Conjugated dienes undergo intermolecular hydroaminoalkylation in the presence of Ti catalyst [Ind2TiMe 2] (Ind=η5-indenyl). This new reaction offers a highly atom-efficient approach to homoallylic amines from 1,3-butadienes. Copyright
Preuss, Till,Saak, Wolfgang,Doye, Sven
p. 3833 - 3837
(2013/04/24)

NOVEL SPIROINDOLINE COMPOUNDS
This invention relates to novel spiroindoline compounds of formula (I) that are generally useful as medicaments, more specifically as medicaments for animals. The medicament can preferably be used for the treatment of helminth infections and the treatment of parasitosis, such as caused by helminth infections. This invention also relates to uses of the compounds to make medicaments and treatments comprising the administration of the compounds to animals in need of the treatments. This invention also relates to the preparation of said compounds. Moreover this invention relates to pharmaceutical compositions and kits comprising the compounds.
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Paragraph 216

(2013/03/26)

Development of a robust reagent for the two-carbon homologation of aldehydes to (E)-α,β-unsaturated aldehydes in water
Synthesis of a new pinacolacetal-phosphonium salt and its reaction with aldehydes to give homologated acetals and two-carbon homologated unsaturated aldehydes is presented. The chemistry takes place in water under mild conditions and the sequence can be performed in one-flask operation.
Mcnulty, James,Zepeda-Velazquez, Carlos,McLeod, David
supporting information
p. 3146 - 3149
(2013/11/06)

Synthesis of novel 1-aryl-9 H -xanthen-9-ones
A novel route for the synthesis of 1-aryl-9H-xanthen-9-ones is reported. This methodology involves the condensation of 2-methylchromone with cinnamaldehydes leading to (E,E)-2-(4-arylbuta-1,3-dien-1-yl)-4H-chromen-4-ones. The final steps involved electrocyclization and oxidation of the latter compounds, in an one-pot synthesis, giving the desired 1-aryl-9H-xanthen-9-ones. Georg Thieme Verlag Stuttgart - New York.
Esteves, Cátia I. C.,Santos, Clementina M. M.,Brito, Cristela M.,Silva, Artur M. S.,Cavaleiro, José A. S.
scheme or table
p. 1403 - 1406
(2011/08/03)

Synthesis of functionalized cinnamaldehyde derivatives by an oxidative heck reaction and their use as starting materials for preparation of Mycobacterium tuberculosis 1-deoxy-d-xylulose-5-phosphate reductoisomerase inhibitors
Cinnamaldehyde derivatives were synthesized in good to excellent yields in one step by a mild and selective, base-free palladium(II)-catalyzed oxidative Heck reaction starting from acrolein and various arylboronic acids. Prepared α,β-unsaturated aldehydes were used for synthesis of novel α-aryl substituted fosmidomycin analogues, which were evaluated for their inhibition of Mycobacterium tuberculosis 1-deoxy-d-xylulose 5-phosphate reductoisomerase. IC50 values between 0.8 and 27.3 μM were measured. The best compound showed activity comparable to that of the most potent previously reported α-aryl substituted fosmidomycin-class inhibitor.
Nordqvist, Anneli,Bjoerkelid, Christofer,Andaloussi, Mounir,Jansson, Anna M.,Mowbray, Sherry L.,Karlen, Anders,Larhed, Mats
experimental part
p. 8986 - 8998
(2011/12/03)

Synthesis and biological activity of desmethoxy analogues of coruscanone A
A series of simple desmethoxy analogues of coruscanone A was prepared via a novel version of Ti(iPrO)4-mediated Knoevenagel condensation of cyclopentenedione with substituted benzaldehydes and cinnamic aldehydes, and the compounds were evaluated for antifungal activity and cytotoxicity. The most potent 2-benzylidenecyclopent-4-ene-1,3-dione possessed antifungal effect comparable to coruscanone A and a somewhat broader spectrum of activity against Candida species. The compound was also superior to fluconazole against several non-albicans Candida sp. Evaluation of the ability of the compound to influence cell proliferation using two different assays showed that 2- benzylidenecyclopent-4-ene-1,3-dione has lower cytotoxicity compared to the natural product.
Tichotová, Lucie,Matou?ová, Eli?ka,?pulák, Marcel,Kune?, Ji?í,Votruba, Ivan,Buchta, Vladimír,Pour, Milan
supporting information; experimental part
p. 6062 - 6066
(2011/11/06)

Emission wavelength prediction of a full-color-tunable fluorescent core skeleton, 9-aryl-1,2-dihydropyrrolo[3,4-b]indolizin-3-one
In this paper we report on a novel fluorescent core skeleton, 9-aryl-1,2-dihydropyrrolo[3,4-b]indolizin-3-one, which we named Seoul-Fluor, having tunable and predictable photophysical properties. Using a concise and practical one-pot synthetic procedure, a 68-member library of new fluorescent compounds was synthesized with diverse substituents. In Seoul-Fluor, the electronic characteristics of the substituents, as well as their positional changes, have a close correlation with their photophysical properties. The systematic perturbation of electronic densities on the specific positions of Seoul-Fluor, guided with the Hammett constant, allows emission wavelength tunability covering the full color range. On the basis of these observations and a computational analysis, we extracted a simple first-order correlation of photophysical properties with the theoretical calculation and accurately predicted the emission wavelength of Seoul-Fluors through the rational design. In this study, we clearly demonstrate that Seoul-Fluor can provide a powerful gateway for the generation of desired fluorescent probes without the need for a tiresome synthesis and trial-and-error process.
Kim, Eunha,Koh, Minseob,Lim, Byung Joon,Park, Seung Bum
supporting information; experimental part
p. 6642 - 6649
(2011/06/19)

Synthesis of 1,3,5-trisubstituted pyrazolines via Zn(ii)-catalyzed double hydroamination of enynes with aryl hydrazines
An efficient Zn(ii)-catalyzed intermolecular double hydroamination of 1,3-enynes with aryl hydrazines, for the synthesis of pyrazolines, has been discussed.
Patil, Nitin T.,Singh, Vipender
supporting information; experimental part
p. 11116 - 11118
(2011/11/29)

Identification of 5-arylidene-4-thiazolidinone derivatives endowed with dual activity as aldose reductase inhibitors and antioxidant agents for the treatment of diabetic complications
In continuing the search for more effective 5-arylidene-4-thiazolidinones as aldose reductase inhibitors, a new set of suitably substituted compounds (4, 5 and 8) was explored. Acetic acids 5, particularly 5a and 5h, proved to be interesting inhibitors of the enzyme as well as excellent antioxidant agents that are potentially able to counteract the oxidative stress associated with both diabetic complications as well as other pathologies. Molecular docking experiments supported SAR studies.
Ottanà, Rosaria,MacCari, Rosanna,Giglio, Marco,Del Corso, Antonella,Cappiello, Mario,Mura, Umberto,Cosconati, Sandro,Marinelli, Luciana,Novellino, Ettore,Sartini, Stefania,La Motta, Concettina,Da Settimo, Federico
experimental part
p. 2797 - 2806
(2011/07/08)

Iron-facilitated direct oxidative C-H transformation of allyl arenes to alkenyl aldehydes
A direct oxidative approach to alkenyl aldehydes from allyl arenes via allyl sp3 C-H functionalization was disclosed. An inexpensive iron catalyst was employed to facilitate this transformation. The mechanistic studies indicate that the cleavage of the allyl sp3 C-H bond is involved in the rate-determining step.
Wang, Teng,Xiang, Shi-Kai,Qin, Chong,Ma, Jun-An,Zhang, Li-He,Jiao, Ning
supporting information; experimental part
p. 3208 - 3211
(2011/06/28)

Facile synthesis of (E)-alkenyl aldehydes from allyl arenes or alkenes via Pd(II)-catalyzed direct oxygenation of allylic C-H bond
Palladium-catalyzed oxygenation of allyl arenes or alkenes has been developed to produce (E)-alkenyl aldehydes with high yields. Allylic C-H bond cleavages occur under the mild conditions during this process. Mechanistic studies show that oxygen source is water.(Figure Presented)
Chen, Huoji,Jiang, Huanfeng,Cai, Congbi,Dong, Jia,Fu, Wei
supporting information; experimental part
p. 992 - 994
(2011/05/08)

Iron(III) chloride-promoted isomerization of propargyl alcohols to α,β-unsaturated carbonyl compounds
Aryl propargyl alcohols bearing a terminal alkynyl moiety can undergo a facile iron(III) chloride-promoted transformation to the corresponding α,β-unsaturated aldehyde in good yield and excellent stereoselectivity.
El Douhaibi, Ahmad Samih,Judeh, Zaher M. A.,Basri, Hedaya,Moussa, Ziad,Messali, Mouslim,Qi, Gao
experimental part
p. 533 - 540
(2011/04/22)

HETEROAROMATIC COMPOUNDS HAVING SPHINGOSINE-1-PHOSPHATE (S1P) RECEPTOR AGONIST BIOLOGICAL ACTIVITY
A novel compound having agonist activity at the S1P3 receptor which is represented by the formula I wherein X is selected from the group consisting of CR3, N and NO;Y is selected from the group consisting of CR3, N and NO;Z is selected from the group consisting of CR3, N and NO; and at least one of X, Y and Z is N or NO; V is O or NOR4 R1 is an aryl group;R2 is an aryl group;R3 is selected from the group consisting of H and alkyl; and 2 of said R3 groups may together form a cyclic alkyl ring having from 3 to 6 carbon atoms; R4 is selected from the group consisting of H and alkyl;a is 0 or an integer of from 1 to 6;b is 0 or 1;c is 0 or 1;f is 0 or an integer of 1 or 2;x is 0 or 1;y is 0 or an integer of from 1 to 3; andz is 0 or an integer of from 1 to 3.
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Page/Page column 21-22

(2008/06/13)

Chromium-carbyne complexes: Intermediates for organic synthesis
(Chemical Equation Presented) On the same route: Chromium-carbyne complexes are readily prepared by treatment of 1,1,1-trichloromethyl reagents with chromium(II) chloride. They serve as intermediates in the selective formation of a wide variety of products, such as alkynes, alkenes, β-hydroxy ketones, aldehydes, allylic alcohols, and allenes (see scheme, E = electrophile).
Bejot, Romain,He, Anyu,Falck, John R.,Mioskowski, Charles
p. 1719 - 1722
(2008/02/13)

Efficient palladium(II) catalysis under air. Base-free oxidative heck reactions at room temperature or with microwave heating
(Figure Presented) Scope and limitations of the base-free oxidative Heck reaction with arylboronic acids have been explored. Under our conditions, the dmphen-palladium(II)-catalyzed arylation proceeded with air or p-benzoquinone as reoxidants of palladium(0). We found that ambient temperature and mild aerobic conditions allow for the use of substrates sensitive to palladium(II)-catalyzed oxidation. Oxidative Heck couplings, employing different arylboronic acids, were smoothly and regioselectively conducted with both electron-rich and electron-poor olefins, providing high yields even with disubstituted butyl methacrylate, sensitive acrolein, and a vinylboronate ester. Controlled microwave processing was used to reduce reaction times from hours to minutes both in small scale and in 50 mmol scale batch processes.
Lindh, Jonas,Enquist, Per-Anders,Pilotti, Ake,Nilsson, Peter,Larhed, Mats
p. 7957 - 7962
(2008/02/13)

4,5-dihydroisoxazoles from arylcyclopropanes: II. Reaction of arylcyclopropanes with nitrosyl chloride activated by sulfur(VI) oxide
Arylcyclopropanes react with nitrosyl chloride activated by sulfur(VI) oxide to give the corresponding 5-aryl-4,5-dihydro-1,2-oxazoles in quantitative yields. The complex NOC1?2SO3 is a highly efficient nitrosating agent which makes it possible to involve in the process arylcyclopropanes having both donor and acceptor substituents in the aromatic ring. Nauka/Interperiodica 2007.
Bondarenko,Gavrilova,Kazantseva,Tikhanushkina,Nifant'ev,Saginova,Zyk
p. 564 - 570
(2008/02/02)

Preparation of optically pure (3E,5E)-alkyl-2-hydroxy-6-arylhexa-3,5-dienoates by Candida parapsilosis ATCC 7330 mediated deracemisation of the racemates
Biocatalytic deracemisation of a range of racemic (3E,5E)-alkyl-2-hydroxy-6-arylhexa-3,5-dienoates using Candida parapsilosis ATCC 7330 resulted in pure (S)-enantiomers in yields of up to 80% and ee>99%.
Thangavel, Vaijayanthi,Chadha, Anju
p. 4126 - 4133
(2007/10/03)