cas 6919-61-5, N-METHOXY-N-METHYLBENZAMIDE

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Development of a Modular Synthetic Route to (+)-Pleuromutilin, (+)-12-epi-Mutilins, and Related Structures
We describe the development of an enantioselective synthetic route to (+)-pleuromutilin (1), (+)-12-epi-mutilin, and related derivatives. A key hydrindanone was prepared in three steps and 48% overall yield from cyclohex-2-en-1-one. 1,4-Hydrocyanation provided a nitrile (53%, or 85% based on recovered starting material) that was converted to the eneimide 57 in 80% yield by the 1,2-addition of methyllithium to the nitrile function, cyclization, and in situ acylation with di-tert-butyldicarbonate. The eneimide 57 was employed in a 2-fold neopentylic coupling reaction with an organolithium reagent derived from the alkyl iodides (R)- or (S)-30, which contain the C11-C13 atoms of the target, to provide diastereomeric diketones in 60% or 48% yield (for coupling with (R)- or (S)-30, respectively). The diketone derived from (S)-30 contains the (S)-C12 stereochemistry found in pleuromutilin and was elaborated to an alkynylaldehyde. Nickel-catalyzed reductive cyclization of this alkynylaldehyde, to construct the eight-membered ring of the target, unexpectedly provided a cyclopentene (67%), which arises from participation of the C12-α-olefin in the transformation. The diketone derived from the enantiomeric C12-fragment (R)-30 underwent reductive cyclization to provide the desired product in 60% yield. This was elaborated to 12-epi-mutilin by a four-step sequence (39% overall). Installation of the glycolic acid residue followed by C12 epimerization (Berner et al. Monatsh. Chem. 1986, 117, 1073) generated (+)-pleuromutilin (1). (+)-12-epi-Pleuromutilin and (+)-11,12-di-epi-pleuromutilin were prepared by related sequences. This work establishes a convergent entry to the pleuromutilins and provides a foundation for the production of novel antibiotics to treat drug-resistant and Gram-negative infections.
Zeng, Mingshuo,Murphy, Stephen K.,Herzon, Seth B.
p. 16377 - 16388
(2017)
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Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst-free synthesis of various substituted amines
Transformation of relatively less reactive functional groups under catalyst-free conditions is an interesting aspect and requires a typical protocol. Herein, we report the synthesis of various primary, secondary, and tertiary amines through hydroboration of amides using pinacolborane under catalyst-free and solvent-free conditions. The deoxygenative hydroboration of primary and secondary amides proceeded with excellent conversions. The comparatively less reactive tertiary amides were also converted to the corresponding N,N-diamines in moderate yields under catalyst-free conditions, although alcohols were obtained as a minor product.
Yi, Jaeeun,Kim, Hyun Tae,Jaladi, Ashok Kumar,An, Duk Keun
supporting information
p. 129 - 132
(2021/11/17)

Asymmetric transfer hydrogenation of heterocycle-containing acetophenone derivatives using N-functionalised [(benzene)Ru(II)(TsDPEN)] complexes
The application of enantiomerically-pure ruthenium(II) catalysts containing N - functionalised TsDPEN ligand to the asymmetric transfer hydrogenation of 15 examples of α-heterocyclic acetophenone derivatives is reported. Products of up to 99% ee were formed.
Barrios-Rivera, Jonathan,Xu, Yingjian,Clarkson, Guy J.,Wills, Martin
supporting information

(2021/12/02)

Z-Selective Fluoroalkenylation of (Hetero)Aromatic Systems by Iodonium Reagents in Palladium-Catalyzed Directed C?H Activation
The direct and catalytic incorporation of fluorine containing molecular motifs into organic compounds resulting high-value added chemicals represents a rapidly evolving part of synthetic methodologies, thus this area is in the focus of pharmaceutical and agrochemical research. Herein we report a stereoselective procedure for direct fluorovinylation of aromatic and heteroaromatic scaffolds. This methodology development has been realized by palladium-catalyzed ortho C?H activation reaction of aniline derivatives featuring the regioselectivity via directing groups such as secondary of tertiary amides, ureas or ketones. The application of non-symmetrical aryl(fluoroalkenyl)-iodonium salts as fluoroalkenylating agents allowed mild reaction conditions in general for this transformation. The scope and limitations have been thoroughly investigated and the feasibility has been demonstrated by more than 50 examples.
Tóth, Balázs L.,Sályi, Gerg?,Domján, Attila,Egyed, Orsolya,Bényei, Attila,Gonda, Zsombor,Novák, Zoltán
p. 348 - 354
(2021/11/09)

Synthesis of 7-Chloroquinoline Derivatives Using Mixed Lithium-Magnesium Reagents
We have prepared a library of functionalized quinolines through the magnesiation of 7-chloroquinolines under mild conditions, employing both batch and continuous flow conditions. The preparation involved the generation of mixed lithium-magnesium intermediates, which were reacted with different electrophiles. Mixed lithium-zinc reagents allowed the synthesis of halogenated and arylated derivatives. Some of the synthesized 4-carbinol quinolines have shown interesting antiproliferative properties, their hydroxyl group being a suitable amino group bioisostere. We also report a two-step approach for optically active derivatives.
Baxendale, Ian R.,Clososki, Giuliano C.,Costa-Lotufo, Leticia V.,Dos Santos, Thiago,Furtado, Luciana C.,Gambacorta, Guido,Moraes De Oliveira, Anderson,Murie, Valter E.,Nicolino, Paula V.,Nishimura, Rodolfo H. V.,Perovani, Icaro S.,Vessecchi, Ricardo
p. 13402 - 13419
(2021/10/12)

Remarkably Efficient Iridium Catalysts for Directed C(sp2)-H and C(sp3)-H Borylation of Diverse Classes of Substrates
Here we describe the discovery of a new class of C-H borylation catalysts and their use for regioselective C-H borylation of aromatic, heteroaromatic, and aliphatic systems. The new catalysts have Ir-C(thienyl) or Ir-C(furyl) anionic ligands instead of the diamine-type neutral chelating ligands used in the standard C-H borylation conditions. It is reported that the employment of these newly discovered catalysts show excellent reactivity and ortho-selectivity for diverse classes of aromatic substrates with high isolated yields. Moreover, the catalysts proved to be efficient for a wide number of aliphatic substrates for selective C(sp3)-H bond borylations. Heterocyclic molecules are selectively borylated using the inherently elevated reactivity of the C-H bonds. A number of late-stage C-H functionalization have been described using the same catalysts. Furthermore, we show that one of the catalysts could be used even in open air for the C(sp2)-H and C(sp3)-H borylations enabling the method more general. Preliminary mechanistic studies suggest that the active catalytic intermediate is the Ir(bis)boryl complex, and the attached ligand acts as bidentate ligand. Collectively, this study underlines the discovery of new class of C-H borylation catalysts that should find wide application in the context of C-H functionalization chemistry.
Chattopadhyay, Buddhadeb,Hassan, Mirja Md Mahamudul,Hoque, Md Emdadul
supporting information
p. 5022 - 5037
(2021/05/04)

Phase-Transfer Catalyzed Asymmetric [4 + 1] Annulations for the Synthesis of Chiral 2,2-Disubstituted Tetrahydrothiophenes
An efficient catalytic asymmetric [4 + 1] reaction, which features the use of simple β-keto esters as one-carbon nucleophiles and 5-succinimidothio-pent-2-enoates as four-atom bielectrophiles, has been developed in the presence of a bifunctional chiral ph
Yin, Qi,Wen, Xiaolu,Chen, Yiwei,Gong, Xiangnan,Hu, Lin
supporting information
p. 7529 - 7534
(2021/10/02)

A Fast and General Route to Ketones from Amides and Organolithium Compounds under Aerobic Conditions: Synthetic and Mechanistic Aspects
We report that the nucleophilic acyl substitution reaction of aliphatic and (hetero)aromatic amides by organolithium reagents proceeds quickly (20 s reaction time), efficiently, and chemoselectively with a broad substrate scope in the environmentally responsible cyclopentyl methyl ether, at ambient temperature and under air, to provide ketones in up to 93 % yield with an effective suppression of the notorious over-addition reaction. Detailed DFT calculations and NMR investigations support the experimental results. The described methodology was proven to be amenable to scale-up and recyclability protocols. Contrasting classical procedures carried out under inert atmospheres, this work lays the foundation for a profound paradigm shift of the reactivity of carboxylic acid amides with organolithiums, with ketones being straightforwardly obtained by simply combining the reagents under aerobic conditions and with no need of using previously modified or pre-activated amides, as recommended.
Ghinato, Simone,Territo, Davide,Maranzana, Andrea,Capriati, Vito,Blangetti, Marco,Prandi, Cristina
supporting information
p. 2868 - 2874
(2021/01/21)

Pd-Catalyzed Double-Decarbonylative Aryl Sulfide Synthesis through Aryl Exchange between Amides and Thioesters
We report the palladium-catalyzed double-decarbonylative synthesis of aryl thioethers by an aryl exchange reaction between amides and thioesters. In this method, amides serve as aryl donors and thioesters are sulfide donors, enabling the synthesis of valuable aryl sulfides. The use of Pd/Xantphos without any additives has been identified as the catalytic system promoting the aryl exchange by C(O)-N/C(O)-S cleavages. The method is amenable to a wide variety of amides and sulfides.
Bie, Fusheng,Cao, Han,Liu, Chengwei,Liu, Xuejing,Shi, Yijun,Szostak, Michal,Zhou, Tongliang
supporting information
p. 8098 - 8103
(2021/10/25)

Rhoda-Electrocatalyzed Bimetallic C?H Oxygenation by Weak O-Coordination
Rhodium-electrocatalyzed arene C?H oxygenation by weakly O-coordinating amides and ketones have been established by bimetallic electrocatalysis. Likewise, diverse dihydrooxazinones were selectively accessed by the judicious choice of current, enabling twofold C?H functionalization. Detailed mechanistic studies by experiment, mass spectroscopy and cyclovoltammetric analysis provided support for an unprecedented electrooxidation-induced C?H activation by a bimetallic rhodium catalysis manifold.
Tan, Xuefeng,Massignan, Leonardo,Hou, Xiaoyan,Frey, Johanna,Oliveira, Jo?o C. A.,Hussain, Masoom Nasiha,Ackermann, Lutz
supporting information
p. 13264 - 13270
(2021/05/06)

Br?nsted Base-Catalyzed Transformation of α,β-Epoxyketones Utilizing [1,2]-Phospha-Brook Rearrangement for the Synthesis of Allylic Alcohols Having a Tetrasubstituted Alkene Moiety
A stereoselective transformation of α,β-epoxyketones into alkenylphosphates having a hydroxymethyl group on the β-carbon was established by utilizing the [1,2]-phospha-Brook rearrangement under Br?nsted base catalysis. The reaction involves the catalytic generation of an α-oxygenated carbanion located at the α-position of an epoxide moiety through the [1,2]-phospha-Brook rearrangement and the following epoxide opening. Further transformation of the alkenylphosphates by the palladium-catalyzed cross-coupling reaction with Grignard reagents provided allylic alcohols having a stereodefined all-carbon tetrasubstituted alkene moiety.
Kondoh, Azusa,Tasato, Naoko,Aoki, Takuma,Terada, Masahiro
supporting information
p. 5170 - 5175
(2020/07/04)

Silylium-Ion-Promoted (5+1) Cycloaddition of Aryl-Substituted Vinylcyclopropanes and Hydrosilanes Involving Aryl Migration
A transition-metal-free (5+1) cycloaddition of aryl-substituted vinylcyclopropanes (VCPs) and hydrosilanes to afford silacyclohexanes is reported. Catalytic amounts of the trityl cation initiate the reaction by hydride abstraction from the hydrosilane, and further progress of the reaction is maintained by self-regeneration of the silylium ions. The new reaction involves a [1,2] migration of an aryl group, eventually furnishing 4- rather than 3-aryl-substituted silacyclohexane derivatives as major products. Various control experiments and quantum-chemical calculations support a mechanistic picture where a silylium ion intramolecularly stabilized by a cyclopropane ring can either undergo a kinetically favored concerted [1,2] aryl migration/ring expansion or engage in a cyclopropane-to-cyclopropane rearrangement.
Bonetti, Vittorio,He, Tao,Klare, Hendrik F. T.,Oestreich, Martin,Wang, Guoqiang
supporting information
p. 12186 - 12191
(2020/05/22)

Organic photochromic dyes and their use for dye-sensitized solar cells
The present invention concerns an organic dye comprising a photochromic entity, a segment -eD representing an electron donor segment and a segment -L-A with -L- representing a covalent bond or a spacer segment and particularly a pi-conjugated spacer segme
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(2020/04/21)

Fluoro-Substituted Methyllithium Chemistry: External Quenching Method Using Flow Microreactors
The external quenching method based on flow microreactors allows the generation and use of short-lived fluoro-substituted methyllithium reagents, such as fluoromethyllithium, fluoroiodomethyllithium, and fluoroiodostannylmethyllithium. Highly chemoselective reactions have been developed, opening new opportunities in the synthesis of fluorinated molecules using fluorinated organometallics.
Colella, Marco,Degennaro, Leonardo,Higuma, Ryosuke,Ishikawa, Susumu,Luisi, Renzo,Nagaki, Aiichiro,Takahashi, Yusuke,Tota, Arianna
supporting information
p. 10924 - 10928
(2020/05/08)

An α-Cyclopropanation of Carbonyl Derivatives by Oxidative Umpolung
The reactivity of iodine(III) reagents towards nucleophiles is often associated with umpolung and cationic mechanisms. Herein, we report a general process converting a range of ketone derivatives into α-cyclopropanated ketones by oxidative umpolung. Mechanistic investigation and careful characterization of side products revealed that the reaction follows an unexpected pathway and suggests the intermediacy of non-classical carbocations.
Bauer, Adriano,Di Mauro, Giovanni,Li, Jing,Maulide, Nuno
supporting information
p. 18208 - 18212
(2020/08/21)

Intramolecular Cyclization of Brominated Oxime Ether Promoted with Ytterbium(0) to the Synthesis of Cyclic Imines
The first utility of ytterbium(0) as a mediating-metal in the intramolecular cyclization of brominated oxime ether was reported in this paper. In contrast to the prior methods, the N–O bond was used as a receptor of nucleophilic reagent, rather than as a source of N-centered radicals. Cyclic imines were obtained in this one-pot reaction with a broad scope of substrates and feasible reaction conditions.
Wang, Yiqiong,Huang, Fei,Zhang, Songlin
supporting information
p. 5178 - 5181
(2020/08/13)

Simple Synthesis of Amides via Their Acid Chlorides in Aqueous TPGS-750-M
The technology of surfactant chemistry is employed for amide bond construction via the reaction of acyl chlorides with amines in 2 wt % TPGS-750-M aqueous solution. Specifically, this highly efficient method enables a chromatography-free scalable process and recycling of the TPGS-750-M solution.
Shi, Min,Ye, Ning,Chen, Wei,Wang, Hui,Cheung, Chiming,Parmentier, Michael,Gallou, Fabrice,Wu, Bin
supporting information
p. 1543 - 1548
(2020/11/23)

Rh-Catalyzed Base-Free Decarbonylative Borylation of Twisted Amides
We report the rhodium-catalyzed base-free decarbonylative borylation of twisted amides. The synthesis of versatile arylboronate esters from aryl twisted amides is achieved via decarbonylative rhodium(I) catalysis and highly selective N-C(O) insertion. The method is notable for a very practical, additive-free Rh(I) catalyst system. The method shows broad functional group tolerance and excellent substrate scope, including site-selective decarbonylative borylation/Heck cross-coupling via divergent N-C/C-Br cleavage and late-stage pharmaceutical borylation.
Bie, Fusheng,Liu, Xuejing,Shi, Yijun,Cao, Han,Han, Ying,Szostak, Michal,Liu, Chengwei,Liu, Xuejing,Szostak, Michal,Liu, Chengwei
p. 15676 - 15685
(2020/11/13)

Synthesis of various acylating agents directly from carboxylic acids
A straightforward synthesis of acylating reagents such as Weinreb and MAP amides from aromatic, aliphatic carboxylic acids, and amino acids using PPh3/NBS combination is described. A chemo-selective modification of the carboxylic acid group into Weinreb amide in the presence of more reactive aldehydes and ketones is presented. All reactions were performed at ambient temperature under air using undried commercial grade solvent. Furthermore, the present methodology could be performed at a gram scale under inert-free reaction conditions. In addition, 7-azaindoline amide auxiliary (used for catalytic asymmetric aldol- and Mannich-type reactions), which behaves like Weinreb amide is also synthesized under similar reaction conditions.
Pilathottathil, Fathima,Vineet Kumar, Doppalapudi,Kaliyamoorthy, Alagiri
supporting information
p. 1622 - 1632
(2020/04/27)

Halide-Accelerated Acyl Fluoride Formation Using Sulfuryl Fluoride
Herein, we report a new one-pot sequential method for SO2F2-mediated nucleophilic acyl substitution reactions starting from carboxylic acids. A mechanistic study revealed that SO2F2-mediated acid activation proceeds via the anhydride, which is then converted to the corresponding acyl fluoride. Tetrabutylammonium chloride or bromide accelerate the formation of acyl fluoride. Optimized halide-accelerated conditions were used to synthesize acyl fluorides in 30-80percent yields, and esters, amides, and thioesters in 72-96percent yields without reoptimization for each nucleophile.
Foth, Paul J.,Malig, Thomas C.,Yu, Hao,Bolduc, Trevor G.,Hein, Jason E.,Sammis, Glenn M.
supporting information
p. 6682 - 6686
(2020/09/02)

Iron-Catalyzed, Iminyl Radical-Triggered Cascade 1,5-Hydrogen Atom Transfer/(5+2) or (5+1) Annulation: Oxime as a Five-Atom Assembling Unit
By integration of iminyl radical-triggered 1,5-hydrogen atom transfer and (5+2) or (5+1) annulation processes, a series of structurally novel and interesting azepine and spiro-tetrahydropyridine derivatives have been successfully prepared in moderate to good yields. This method utilizes FeCl2 as the catalyst and readily available oximes as five-atom units, while showcasing broad substrate scope and good functional group compatibility. The annulation products can be easily converted into many valuable compounds. Moreover, DFT calculation studies are performed to provide some insights into the possible reaction mechanisms for the (5+2) and (5+1) annulations.
Chen, Ying-Chun,Du, Fei,Jiang, Kun,Liang, Wu,Ouyang, Qin,Shuai, Li,Wei, Ye,Yang, Jie
supporting information
p. 19222 - 19228
(2020/08/25)

Saturated Bioisosteres of ortho-Substituted Benzenes
Saturated bioisosteres of ortho-disubstituted benzenes (bicyclo[2.1.1]hexanes) were synthesized, characterized and validated. These cores were incorporated into the bioactive compounds Valsartan, Boskalid and Fluxapyroxad instead of the benzene ring. The
Denisenko, Aleksandr,Garbuz, Pavel,Mykhailiuk, Pavel K.,Shishkina, Svetlana V.,Voloshchuk, Nataliya M.
supporting information
p. 20515 - 20521
(2020/08/21)

Formation of Aryl [1-Cyano-4-(dialkylamino)butadienyl] Ketones from Pyridines
Treatment of 2-chloropyridine with LDA and the Weinreb amide of benzoic acid afforded three unusual products, namely N -methylbenzamide, 2-chloropyridine-3-methanol, and the ring-opened addition product. This same final product could also be obtained from 2-chloro-3-benzoylpyridine on treatment with LDA. Mechanistic insight for the formation of these products is provided.
Gim, Hyo Jin,Jung, Michael E.
supporting information
p. 2548 - 2552
(2019/06/08)

Electrochemically Promoted Fluoroalkylation-Distal Functionalization of Unactivated Alkenes
Difunctionalization of olefins represents a powerful synthetic tool and yet a challenging task. This work describes an electrochemically enabled fluoroalkylation-migration reaction of unactivated olefins in the absence of a strong oxidant or heavy metal catalyst, affording fluorinated (hetero)aryl ketones in good yields and excellent regioselectivities. The efficient and sustainable electrochemical strategy provides a rapid access to a dual functionalized fluorine-containing heterocyclic manifold.
Zou, Zhenlei,Zhang, Weigang,Wang, Yang,Kong, Lingyu,Karotsis, Georgios,Wang, Yi,Pan, Yi
supporting information
p. 1857 - 1862
(2019/03/11)

One-pot synthesis of Weinreb amides employing 3,3-dichloro-1,2-diphenylcyclopropene (CPI-Cl) as a chlorinating agent
The synthesis of Nα-protected amino alkyl Weinreb amides starting from the corresponding α-amino acids as well as carboxylic acids has been delineated through the in situ generation of acid chlorides using CPI-Cl as a chlorinating agent. The protocol is simple; the reaction conditions employed were mild, and compatible with all the three commonly used urethane protecting groups namely, Boc, Cbz and Fmoc groups. The resulting Weinreb amides are obtained in good yields as optically pure products.
Shekharappa,Roopesh Kumar,Sureshbabu, Vommina V.
supporting information
p. 790 - 798
(2019/03/26)

Iminyl Radicals by Reductive Cleavage of N-O Bond in Oxime Ether Promoted by SmI2: A Straightforward Synthesis of Five-Membered Cyclic Imines
A new generation method of N-centered radicals from the reductive cleavage of the N-O bond in oxime ether promoted by SmI2 is reported for the first time. The in-situ-generated N-centered radicals underwent intramolecular cyclization to afford five-membered cyclic imines in two manners: N-centered radical addition and N-centered anion nucleophilic substitution. From a synthetic point of view, an efficient synthetic method of five-membered cyclic imines was developed. A mechanism of the transformation was proposed.
Huang, Fei,Zhang, Songlin
supporting information
p. 7430 - 7434
(2019/10/11)

COMPOUNDS AS MODULATORS OF TLR2 SIGNALING
The present disclosure relates to compounds, pharmaceutical compositions comprising such compounds, and use of such compounds in methods of treatment or in medicaments for treatment of inflammatory diseases and certain neurological disorders that are related to inflammatory signaling processes, including but not limited to misfolded proteins.
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(2019/10/23)

Broadly Applicable Ytterbium-Catalyzed Esterification, Hydrolysis, and Amidation of Imides
An efficient, broadly applicable, operationally simple, and divergent process for the transformation of imides into a range of carboxylic acid derivatives under mild conditions is reported. By simply using catalytic amounts of ytterbium(III) triflate as a Lewis acid promoter in the presence of alcohols, water, amines, or N,O-dimethylhydroxylamine, a broad range of imides is smoothly and readily converted to the corresponding esters, carboxylic acids, amides, and Weinreb amides in good yields. This method notably enables an easy cleavage of oxazolidinone-based auxiliaries.
Guissart, Céline,Barros, Andre,Rosa Barata, Luis,Evano, Gwilherm
supporting information
p. 5098 - 5102
(2018/09/13)

Palladium-Catalyzed, ortho-Selective C-H Halogenation of Benzyl Nitriles, Aryl Weinreb Amides, and Anilides
A palladium-catalyzed, ortho-selective C-H halogenation methodology is reported herein. The highlight of the work is the highly selective C(sp2)-H functionalization of benzyl nitriles in the presence of activated C(sp3)-H bond, which results in good yields of the halogenated products with excellent regioselectivity. Along with benzyl nitriles, aryl Weinreb amides and anilides have been evaluated for the transformation using aprotic conditions. Mechanistic studies yield interesting aspects with respect to the pathway of the reaction and the directing group abilities.
Das, Riki,Kapur, Manmohan
p. 1114 - 1126
(2018/06/18)

Synthesis of Difluoromethyl Ketones from Weinreb Amides, and Tandem Addition/Cyclization of o-Alkynylaryl Weinreb Amides
[Difluoro(phenylsulfanyl)methyl]trimethylsilane (PhSCF2SiMe3) underwent a fluoride-induced nucleophilic addition to the carbonyl group of Weinreb amides to provide the corresponding difluoro(phenylsulfanyl)methyl ketones. These were
Phetcharawetch, Jongkonporn,Betterley, Nolan M.,Soorukram, Darunee,Pohmakotr, Manat,Reutrakul, Vichai,Kuhakarn, Chutima
supporting information
p. 6840 - 6850
(2017/12/26)

Cleavage of 1,3-dicarbonyls through oxidative amidation
A mild and convenient protocol for the oxidative cleavage of 1,3-diketone compounds is described. Under metal-free conditions, the method converts the 1,3-dicarbonyls into amides when treated with (nBu4N)N3 and iodine in the presence of an amine at room temperature. Using this method, a range of 1,3-dicarbonyls with various structural motifs including sterically demanding substituents and ordinary functional groups were easily fragmented, and it is demonstrated that cyclic 1,3-dicarbonyls can be directly transformed into acyclic diamides through ring-opening. Initial mechanistic studies show that diazidation of the enol form is followed by nucleophilic substitution with the amine.
Biallas, Phillip,H?ring, Andreas P.,Kirsch, Stefan F.
supporting information
p. 3184 - 3187
(2017/04/21)

Mo(CO)6 as a Solid CO Source in the Synthesis of Aryl/Heteroaryl Weinreb Amides under Microwave-Enhanced Condition
The facile transformation of aryl/heteroaryl nonaflates into corresponding amides via Pd-catalyzed aminocarbonylation using Mo(CO)6 as a solid CO source under microwave-enhanced condition is reported. The method was found to be tolerant with respect to a
Ningegowda, Raghu,Bhaskaran, Savitha,Sajith, Ayyiliath M.,Aswathanarayanappa, Chandrashekar,Padusha, M. Syed Ali,Priya, Babu Shubha
p. 44 - 51
(2017/01/21)

Solvent-Controlled, Tunable β-OAc and β-H Elimination in Rh(III)-Catalyzed Allyl Acetate and Aryl Amide Coupling via C-H Activation
The Heck reaction between arenes and allyl acetate has led to cinnamyl derivatives and allyl products depending on the regioselectivity of β-elimination. The regioselectivity can be controlled by the solvent in the Rh(III)-catalyzed arene-allyl acetate coupling via C-H activation: (1) in THF, cinnamyl derivatives via β-H elimination were generated; (2) in MeOH, allyl products via β-OAc elimination were produced. Both routes have advantages such as excellent γ-selectivity toward allyl acetate, good to excellent yields, and broad substrate scope.
Dai, Huimin,Yu, Chao,Wang, Zihao,Yan, Hong,Lu, Changsheng
supporting information
p. 3410 - 3413
(2016/07/26)

Radical-Mediated 1,2-Formyl/Carbonyl Functionalization of Alkenes and Application to the Construction of Medium-Sized Rings
A novel radical 1,2-formylfunctionalization of alkenes involving 1,2(4,5)-formyl migration triggered by addition of various carbon- and heteroatom-centered radicals to alkenes has been developed for the first time, thus providing straightforward access to diverse β-functionalized aldehydes with good efficiency, remarkable selectivity, and excellent functional group tolerance. Analogous transformations mediated by a keto-carbonyl migration have also been effected under similar conditions. This method was used to access ring systems including various benzannulated nine-, ten-, and eleven-membered rings, complex 6-5(6,7)-6(5) fused rings, and bridged rings with diverse functionalities.
Li, Zhong-Liang,Li, Xiao-Hua,Wang, Na,Yang, Ning-Yuan,Liu, Xin-Yuan
supporting information
p. 15100 - 15104
(2016/11/25)

N-Methoxy-N-methylcyanoformamide, a Highly Reactive Reagent for the Formation of β-Keto Weinreb Amides and Unsymmetrical Ketones
A rapid and straightforward synthesis of the new and highly reactive reagent N-methoxy-N-methylcyanoformamide from trimethylsilyl cyanide and N-methoxy-N-methylcarbamoylimidazole, is reported. This reagent enables the one-pot preparation of β-carbonyl Wei
Nugent, Jeremy,Schwartz, Brett D.
supporting information
p. 3834 - 3837
(2016/08/16)

Palladium-Catalyzed Deaminative Phenanthridinone Synthesis from Aniline via C-H Bond Activation
This work reports palladium-catalyzed phenanthridinone synthesis using the coupling of aniline and amide by formation of C-C and C-N bonds in a one-pot fashion via dual C-H bond activation. It involves simultaneous cleavage of four bonds and the formation of two new bonds. The present protocol is ligand-free, takes place under mild reaction conditions, and is environmentally benign as nitrogen gas and water are the only side products. This transformation demonstrates a broad range of aniline and amide substrates with different functional groups and has been scaled up to gram level.
Yedage, Subhash L.,Bhanage, Bhalchandra M.
supporting information
p. 4103 - 4111
(2016/06/09)

Palladium-catalyzed Suzuki-Miyaura coupling of amides by carbon-nitrogen cleavage: General strategy for amide N-C bond activation
The first palladium-catalyzed Suzuki-Miyaura cross-coupling of amides with boronic acids for the synthesis of ketones by sterically-controlled N-C bond activation is reported. The transformation is characterized by operational simplicity using bench-stable, commercial reagents and catalysts, and a broad substrate scope, including substrates with electron-donating and withdrawing groups on both coupling partners, steric-hindrance, heterocycles, halides, esters and ketones. The scope and limitations are presented in the synthesis of >60 functionalized ketones. Mechanistic studies provide insight into the catalytic cycle of the cross-coupling, including the first experimental evidence for Pd insertion into the amide N-C bond. The synthetic utility is showcased by a gram-scale cross-coupling and cross-coupling at room temperature. Most importantly, this process provides a blueprint for the development of a plethora of metal catalyzed reactions of typically inert amide bonds via acyl-metal intermediates. A unified strategy for amide bond activation to enable metal insertion into N-C amide bond is outlined (Scheme 1).
Meng, Guangrong,Szostak, Michal
supporting information
p. 5690 - 5707
(2016/07/06)

Catalytic Diverse Radical-Mediated 1,2-Cyanofunctionalization of Unactivated Alkenes via Synergistic Remote Cyano Migration and Protected Strategies
A catalytic radical protocol for 1,2-cyanofunctionalization of unactivated alkenes involving remote cyano migration triggered by addition of diverse carbon- and heteroatom-centered radicals to alkenes has been developed. This powerful strategy provides a
Wang, Na,Li, Lei,Li, Zhong-Liang,Yang, Ning-Yuan,Guo, Zhen,Zhang, Hong-Xia,Liu, Xin-Yuan
supporting information
p. 6026 - 6029
(2016/12/09)

A new strategy for accessing (S)-1-(furan-2-yl)pent-4-en-1-ol: a key precursor of Ipomoeassin family of compounds and C1–C15 domain of halichondrins
A highly efficient synthesis of (S)-1-(furan-2-yl)pent-4-en-1-ol, known to be an initial precursor of Ipomoeassin family of compounds and C1–C15 domain of halichondrins has been achieved via a sequence involving the use of Weinreb amide formation followed by Weinreb ketone synthesis and finally CBS (Corey–Bakshi–Shibata) reduction. Detailed study on improvement of each step is described. The title compound was converted to a potential cytotoxic agent for further pharmacological studies.
Jammula, Subba Rao,Anna, Venkateswara Rao,Tatina, Sudhakar,Krishna, Thalishetti,Sreenivas, B. Yogi,Pal, Manojit
supporting information
p. 3924 - 3928
(2016/08/09)

An Environmentally Sustainable Mechanochemical Route to Hydroxamic Acid Derivatives
An operationally simple, and cost efficient conversion of carboxylic acids into hydroxamic acid derivatives via a high-energy mechanochemical activation is presented. This ball milling methodology was applied to a wide variety of carboxylic acids dramatically improving purification issues associated with this class of molecules, which still remain one of the main bottlenecks of classical methodologies. (Figure presented.).
Mocci, Rita,De Luca, Lidia,Delogu, Francesco,Porcheddu, Andrea
supporting information
p. 3135 - 3144
(2016/10/09)

High-Yield Lithiation of Azobenzenes by Tin-Lithium Exchange
The lithiation of halogenated azobenzenes by halogen-lithium exchange commonly leads to substantial degradation of the azo group to give hydrazine derivatives besides the desired aryl lithium species. Yields of quenching reactions with electrophiles are therefore low. This work shows that a transmetalation reaction of easily accessible stannylated azobenzenes with methyllithium leads to a near-quantitative lithiation of azobenzenes in para, meta, and ortho positions. To investigate the scope of the reaction, various lithiated azobenzenes were quenched with a variety of electrophiles. Furthermore, mechanistic 119Sn NMR spectroscopic studies on the formation of lithiated azobenzenes are presented. A tin ate complex of the azobenzene was detected and characterized at low temperature.
Strueben, Jan,Lipfert, Matthias,Springer, Jan-Ole,Gould, Colin A.,Gates, Paul J.,S?nnichsen, Frank D.,Staubitz, Anne
supporting information
p. 11165 - 11173
(2015/11/10)

Silver-mediated oxidative aliphatic C-H trifluoromethylthiolation
The first example of a practical and direct trifluoromethylthiolation reaction of unactivated aliphatic C-H bonds employs a silver-based reagent. The reaction is operationally simple, scalable, and proceeds under aqueous conditions in air. Furthermore, its broad scope and good functional-group compatibility were demonstrated by applying this method to the selective trifluoromethylthiolation of natural products and natural-product derivatives.
Guo, Shuo,Zhang, Xiaofei,Tang, Pingping
supporting information
p. 4065 - 4069
(2015/03/30)

Reductive N-O cleavage of Weinreb amides by sodium in alumina and silica gels: synthetic and mechanistic studies
The use of sodium in alumina and silica gels for the reductive cleavage of the N-O bond of N-methoxy-N-methylamides, commonly referred to as Weinreb amides, has been investigated. This method reduces a diverse set of Weinreb amides with different function
Jackson, James E.,O'Brien, Brittany N.,Kedzior, Sonya K.,Fryz, Gage R.,Jalloh, Fatmata S.,Banisafar, Arash,Caldwell, Michael A.,Braun, Max B.,Dunyak, Bryan M.,Dye, James L.
supporting information
p. 6227 - 6230
(2015/10/20)

A mild and efficient amide formation reaction mediated by P(OEt)3 and iodine
With the activation of P(OEt)3 and I2, carboxylic acids can smoothly react with various primary and secondary amines, affording a series of amides, including peptides without racemization. 31P NMR spectroscopy studies showed that carboxylic phosphoric mixed anhydride was the reactive intermediate and a possible mechanism was herein proposed.
Chen, Pei-Jiang,Wang, Hai-Yang,Peng, Ai-Yun
p. 94328 - 94331
(2015/11/17)

One-Pot Direct Synthesis of Weinreb Amides from Aryl and Hetero Aryl Halides Using Co 2(CO) 8 as an Effective CO Source under Conventional Thermal Heating
A successful protocol for the synthesis of Weinreb amides directly from aryl halides via aminocarbonylation with N,O-dimethyl hydroxylamine using Co2(CO)8 as an in situ CO source has been demonstrated. The effects of various reaction parameters such as temperature, base, and CO source have also been investigated and optimized. GRAPHICAL ABSTRACT.
Baburajan, Poongavanam,Elango, Kuppanagounder P.
p. 541 - 548
(2015/10/29)

Copper-catalyzed synthesis of weinreb amides by oxidative amidation of alcohols
A simple and efficient protocol has been developed for the oxidative amidation of alcohols to Weinreb amides using tert-butyl hydroperoxide as an oxidant and an inexpensive and air stable copper catalyst. The present protocol is advantageous as it uses commercially affordable alcohols as starting materials. The developed protocol also tolerates various substituted alcohols as starting materials to provide good to excellent yields of the desired products.
Yedage, Subhash L.,Bhanage, Bhalchandra M.
p. 526 - 532
(2015/02/19)

Easy, Green and Safe Carbonylation Reactions through Zeolite-Catalyzed Carbon Monoxide Production from Formic Acid
Zeolites with the right shape and acid site density and strength, such as certain ZSM-5 forms, were able to cleanly decompose formic acid to carbon monoxide (CO), and the latter could be directly used in palladium-catalyzed carbonylation reactions. A simple two-reactor system was designed to produce CO conveniently and then further react this gas in a safe way. The two-reactor system is particularly cheap, easy to set up and use. In addition, the carbonylation conditions without pressure allowed for very efficient CO incorporation, with only 1% of palladium(II) chloride (PdCl2) and Xantphos.
Losch, Pit,Felten, Anne-Sophie,Pale, Patrick
supporting information
p. 2931 - 2938
(2015/09/28)

An Efficient synthesis of Weinreb amides and ketones via palladium nanoparticles on ZIF-8 catalysed carbonylative coupling
Heterogeneously catalysed carbonylative coupling reactions such as aminocarbonylation and Suzuki-carbonylation are reported using Pd nanoparticles supported on ZIF-8 for efficient and environmentally attractive synthesis of Weinreb amides and ketones from aryl bromides or iodides. The catalyst is air stable, offers high activity with very low palladium leaching and is recyclable. The presence of a phosphine ligand was required when aryl bromides were used as substrates, while no ligand was necessary when aryl iodides were used. the Partner Organisations 2014.
Thanh Dang, Tuan,Chen, Anqi,Majeed Seayad, Abdul
p. 30019 - 30027
(2014/08/05)

Synthesis of a photocontrollable hydrogen sulfide donor using ketoprofenate photocages
We report the design, synthesis and application of a directly photocontrollable hydrogen sulfide (H2S) donor, which releases H 2S proportionally to the intensity and duration of photoirradiation. Photocontrolled H2S releas
Fukushima, Naoki,Ieda, Naoya,Sasakura, Kiyoshi,Nagano, Tetsuo,Hanaoka, Kenjiro,Suzuki, Takayoshi,Miyata, Naoki,Nakagawa, Hidehiko
supporting information
p. 587 - 589
(2014/01/06)

Design and synthesis of epicocconone analogues with improved fluorescence properties
Epicocconone is a natural latent fluorophore that is widely used in biotechnology because of its large Stokes shift and lack of fluorescence in its unconjugated state. However, the low photostability and quantum yields of epicocconone have limited its wid
Peixoto, Philippe A.,Boulang, Agathe,Ball, Malcolm,Naudin, Bertrand,Alle, Thibault,Cosette, Pascal,Karuso, Peter,Franck, Xavier
p. 15248 - 15256
(2014/12/11)