Article
Chemistry, Organic
Iliyasu Aliyu Bashir, Sunwoo Lee
Summary: Symmetrical anhydrides can be synthesized from activated amides such as N-benzoylsaccharins and N-Boc-protected benzamides. The reaction of activated amides with H2O in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) at 25 degrees C can efficiently cleave the C-N bond and yield the corresponding symmetrical anhydrides in high yields. Additionally, N-benzoylsaccharins can react with benzoic acid derivatives to generate unsymmetrical anhydrides in high yields.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Yukun Chen, Xiaoxiang Xi, Weiming Yuan
Summary: A photoinduced nickel-catalyzed reductive acyl-coupling reaction has been developed, enabling the synthesis of sterically bulky alpha-tertiary ketones. The reaction does not require an exogenous photocatalyst or a metal reductant, and various unstrained tertiary acyl electrophiles can be coupled with alkyl radicals under mild conditions, leading to the formation of all carbon quaternary aliphatic ketones, including alpha-tertiary amino ketones.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Wataru Ishiga, Masaya Ohta, Takuya Kodama, Mamoru Tobisu
Summary: This study demonstrates a catalytic ortho to para transposition of a silyl group in aniline derivatives using [RuCl2(p-cymene)](2)/BINAP in conjunction with a Cu(OAc)(2) additive. The method is also effective in isomerizing 2-silylpyrrole derivatives to their corresponding 3-silyl isomers.
Article
Chemistry, Multidisciplinary
Xue-Ya Gou, Yuke Li, Wei-Yu Shi, Yu-Yong Luan, Ya-Nan Ding, Yang An, Yan-Chong Huang, Bo-Sheng Zhang, Xue-Yuan Liu, Yong-Min Liang
Summary: This paper describes a new ruthenium-catalyzed method for the ortho- and meta-C-Ar-H glycosylation, resulting in the synthesis of various C-aryl pyranosides and furanosides. The method shows broad substrate scope and compatibility with different N-heterocyclic directing groups. Mechanistic studies suggest different pathways for ortho- and meta-C-Ar-H glycosylation, and density functional theory calculations provide an explanation for the high stereoselectivity observed in the meta-C-Ar-H glycosylation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Wei-Hao Rao, Qi Li, Li-Li Jiang, Ying-Ge Li, Pan Xu, Xue-Wan Deng, Ming Li, Guo-Dong Zou, Xinhua Cao
Summary: An acyl lactonization of alkenes with aldehydes under visible-light photoredox catalysis was described, showing broad scope and good functional group tolerance with isolated yields ranging from 50-95%. Mechanistic studies revealed that the transformation proceeds via a radical chain process.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Amal Benzai, Fazia Derridj, Henri Doucet, Jean-Francois Soule
Summary: The study reports a Pd- or Ru-catalyzed arylation reaction that allows for the ortho-arylation of the aryl unit of 2-arylpyrazines with high regioselectivity and applicability to various substituted pyrazine compounds. Experimental results demonstrate that even pyrazines with 2,3-diphenyl substitution can yield the desired arylated product.
Article
Chemistry, Organic
Bin-Qing He, Yuan Gao, Peng-Zi Wang, Hong Wu, Hong-Bin Zhou, Xiao-Peng Liu, Jia-Rong Chen
Summary: An unprecedented dual photoredox/palladium-catalyzed reaction using oxime esters for C-C bond cleavage and directed ortho C-H acylation of 2-arylpyridines has been described. This redox-neutral protocol demonstrates excellent regioselectivity, broad substrate scope, and good functional-group tolerance, resulting in a range of aryl ketones with generally good yields.
Article
Chemistry, Multidisciplinary
Yi Liu, Cuihan Zhou, Meijing Jiang, Bruce A. Arndtsen
Summary: We have developed a general palladium-catalyzed method to synthesize acyl fluorides from different types of compounds. Mechanistic analysis suggests that the reaction proceeds through the combination of visible light photoexcitation of Pd(0) with a ligand-favored reductive elimination, resulting in a unidirectional catalytic cycle. Coupling this catalytic method with nucleophilic reactions allows for a broad range of carbonylation reactions, including the synthesis of highly functionalized products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Yi-Xin Xu, Yu-Qing Liang, Zhong-Jian Cai, Shun-Jun Ji
Summary: A novel chelation-assisted C-H arylation reaction of benzo[h]quinoline is described in this study. The reaction, using [RuCl2(p-cymene)]2 as the catalyst and cheap and easily accessible arylsulfonyl chlorides as the arylation source, exhibits simple reaction conditions, a broad substrate scope, and good functional group tolerance. The successful application of bioactive-molecule-based sulfonyl chlorides further emphasizes the potential utility and importance of this desulfitative C-H arylation protocol.
Article
Chemistry, Organic
Mengna Liu, Benqiang Cui, Chuntao Zhong, Yanhui Shi, Yanfeng Dang, Changsheng Cao
Summary: A palladium-catalyzed cyanation of aryl dimethylsulfonium salts using K-4[Fe-(CN)(6)]center dot 3H(2)O as the cyanating reagent was successfully developed. The reaction proceeded under base-free conditions and yielded aryl nitriles with up to 92% yields. The protocol also allowed direct transformation of aryl sulfides to aryl nitriles, and the reaction mechanism was investigated using density functional theory calculations.
Article
Chemistry, Organic
Xiaofeng Liu, Ying Shao, Jiangtao Sun
Summary: A ruthenium-catalyzed highly chemoselective N-alkylation of 2-pyridones has been developed, providing N-alkylated 2-pyridone derivatives in good yields and excellent N-selectivity. The key to this unprecedented reaction is the use of CpRu(PPh3)(2)Cl as the catalyst and sulfoxonium ylides as the alkylation reagents, which can also be applied to 7-azaindoles with slight variations in reaction conditions. Furthermore, sulfonium ylides are also suitable alkylation reagents for good selectivity in N-alkylation of 2-pyridones.
Article
Chemistry, Organic
Yong Liu, Yuenian Xu, Yan Zhang, Wen-Chao Gao, Xinxin Shao
Summary: A highly efficient cross-electrophile coupling of organic halides with thiol-free synthesized N-thiophthalimides as direct thiolating surrogates was presented. This strategy avoids the use of odorous and toxic thiols and features low catalyst loading, good functional group tolerance, and diverse downstream synthesis.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Yonggang Yan, Jinjin Sun, Gang Li, Liu Yang, Wei Zhang, Rui Cao, Chao Wang, Jianliang Xiao, Dong Xue
Summary: A light-promoted Ni-catalyzed cyanation reaction using 1,4-dicyanobenzene as a cyanating agent is described. Various aryl bromides, chlorides, and druglike molecules are converted to their corresponding nitriles (65 examples). Mechanistic studies reveal that under irradiation, the Ni(II)(dtbbpy)(p-C6H4CN)(CN) oxidative addition product undergoes homolytic cleavage of the Ni-aryl bond to generate an aryl radical and a Ni(I)-CN species, which initiates subsequent cyanation reactions.
Article
Chemistry, Organic
Wei-Hao Rao, Qi Li, Ying-Ge Li, Li-Li Jiang, Ming-Xiao Yue, Guo-Dong Zou, Xinhua Cao
Summary: A photocatalytic acyl lactonization of unsaturated carboxylic acids using inexpensive acyl chlorides has been developed, allowing for modular synthesis of acyl lactones. The method efficiently constructs biologically important phthalide frameworks and is applicable to a wide variety of unsaturated carboxylic acids and aroyl, heteroaroyl chlorides. The survival of functional groups including MeO, F, Cl, and Br suggests a free radical pathway in the reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Fusheng Bie, Xuejing Liu, Han Cao, Yijun Shi, Tongliang Zhou, Michal Szostak, Chengwei Liu
Summary: The Pd-catalyzed double-decarbonylative synthesis of aryl thioethers involves an aryl exchange reaction between amides and thioesters, with amides serving as aryl donors and thioesters as sulfide donors. The use of Pd/Xantphos without any additives promotes aryl exchange by C(O)-N/C(O)-S cleavages, allowing for a wide variety of amides and sulfides to be used in the reaction.
Article
Chemistry, Multidisciplinary
Takuya Kochi, Kazuya Ichinose, Masayuki Shigekane, Taro Hamasaki, Fumitoshi Kakiuchi
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Multidisciplinary
Hikaru Kondo, Takuya Kochi, Fumitoshi Kakiuchi
CHEMISTRY-A EUROPEAN JOURNAL
(2020)
Article
Chemistry, Organic
Issei Suzuki, Hikaru Kondo, Takuya Kochi, Fumitoshi Kakiuchi
JOURNAL OF ORGANIC CHEMISTRY
(2019)
Article
Chemistry, Multidisciplinary
Shotaro Takano, Ryosuke Shiomi, Yoshihiko Morimoto, Takuya Kochi, Fumitoshi Kakiuchi
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Organic
Seiya Terai, Yuki Sato, Takuya Kochi, Fumitoshi Kakiuchi
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Multidisciplinary
Shunsuke Onodera, Ryo Togashi, Soya Ishikawa, Takuya Kochi, Fumitoshi Kakiuchi
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2020)
Review
Chemistry, Multidisciplinary
Fumitoshi Kakiuchi, Takuya Kochi
Article
Chemistry, Organic
Yoshihiko Morimoto, Moe Hamada, Shotaro Takano, Katsufumi Mochizuki, Takuya Kochi, Fumitoshi Kakiuchi
Summary: Utilizing 8-quinolinolato rhodium catalysts and CsF, the coupling of alkylacetylenes with secondary amines in both 2:1 and 1:1 ratios was achieved. The solvent choice can switch the selectivity between 2:1 and 1:1 ratios, leading to different products under different reaction conditions.Additionally, anti-Markovnikov hydroamination reactions in toluene resulted in 1:1 coupling products under relatively mild conditions.
Article
Chemistry, Multidisciplinary
Fumitoshi Kakiuchi, Takuya Kochi
Summary: In this account, the authors discussed their efforts in palladium-catalyzed electrochemical C-H functionalizations, including C-H halogenations using different halogen sources, a one-pot synthesis method, and an iodine-mediated oxidative homo-coupling reaction of arylpyridines.
Article
Chemistry, Multidisciplinary
Naoki Kimura, Shiori Katta, Yoichi Kitazawa, Takuya Kochi, Fumitoshi Kakiuchi
Summary: A new method for the C-H homoallylation reaction of aromatic ketones with methylenecyclopropanes using a catalytic amount of Fe(PMe3)(4) was reported, yielding selectively ortho-homoallylated aromatic ketones through regioselective scission of the three-membered rings. The homoallylated products are suitable for further modifications, leading to functionalized 1,2-dihydronaphthalenes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Naoki Kimura, Shiori Katta, Yoichi Kitazawa, Takuya Kochi, Fumitoshi Kakiuchi
Summary: Deuterium-labeling experiments were conducted for Fe(PMe3)(4)-catalyzed C-H/olefin coupling using a deuterium-labeled aromatic ketone and various alkenes. The choice of alkene significantly affects the reversible 2,1-insertion process during the reaction. While no H/D scrambling was detected for reactions with vinylsilane and N-vinylcarbazole, significant levels of H/D scrambling were observed for reactions with styrenes, suggesting rapid 2,1-insertion/beta-elimination processes.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Kazuma Muto, Takaaki Kumagai, Fumitoshi Kakiuchi, Takuya Kochi
Summary: Palladium-catalyzed remote arylative substitution was achieved for the reaction of arylboronic acids with alkenes possessing a distant acetoxy group, providing arylation products with an alkene moiety at the remote position with good regioselectivity. This reaction is applicable to various arylboronic acids and alkene substrates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yoshihiko Morimoto, Takuya Kochi, Fumitoshi Kakiuchi
Summary: The anti-Markovnikov addition of anilines to aliphatic terminal alkynes was achieved using an 8-quinolinolato rhodium/phosphine catalyst system, with the formation of aldimine products facilitated by the use of a strong organic base, 1,1,3,3,-tetramethylguanidine. Substrates with various functional groups, including polar groups like phenolic hydroxy group, are suitable for hydroamination.
HELVETICA CHIMICA ACTA
(2021)
Article
Chemistry, Organic
Yoshihiko Morimoto, Takuya Kochi, Fumitoshi Kakiuchi
Summary: A new catalytic system was developed for the anti-Markovnikov hydroamination of both aliphatic and aromatic terminal alkynes with primary amines, yielding high amounts of aldimines and enamines. This system exhibited high functional group tolerance, including hydroxy, bromo, cyano, and thioester groups.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Shota Kanno, Fumitoshi Kakiuchi, Takuya Kochi
Summary: A novel catalytic method using chain walking and dimetal reagents was developed for the remote bismetalation of alkene substrates, resulting in cyclopentane derivatives with two boryl groups at remote positions. The regioselective transformation of an unactivated sp(3) C-H bond to a C-B bond successfully achieved the sequential construction of three distant bonds for 1,n-dienes (n >= 7).
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
