Article
Chemistry, Organic
Shogo Nakamura, Soshi Nishino, Koji Hirano
Summary: A copper-catalyzed regioselective hydroamination method was developed to synthesize alpha-aminophosphonates from alpha,beta-unsaturated phosphonates, which are of interest in medicinal chemistry. The use of an umpolung, electrophilic amination strategy with a hydroxylamine derivative is key to achieving the desired regioselectivity, as compared to the conventional nucleophilic hydroamination conditions with the parent amine. The article also discusses the asymmetric synthesis using a chiral bisphosphine ligand and its application in a related silylamination reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Shiyuan Wu, Qiuting Zhao, Chao Wu, Chengming Wang, Hao Lei
Summary: A novel and highly efficient transition-metal-free approach for the conversion of alpha-bromoanilides to 3,3-disubstituted oxindoles is described. The transformation exhibits good functional group tolerance and is most likely a radical process.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Young Ho Kim, Dong Bin Kim, Su San Jang, So Won Youn
Summary: A Pd-catalyzed intramolecular allylic C-H amination method has been developed, allowing for the synthesis of diverse 1,3-X,N-heterocycles through selective allylic C-H cleavage and pi-allylpalladium formation. The use of substrates containing a labile allylic moiety and new catalytic systems overcomes significant challenges for achieving highly chemo- and regioselective allylic C-H amination.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Toshimichi Kobayashi, Soshi Nishino, Masahiro Miura, Koji Hirano
Summary: A copper-catalyzed silylamination reaction has been developed for the synthesis of β-silyl-α-amino acid derivatives, which are of great interest in medicinal and pharmaceutical chemistry. The use of a suitable chiral ligand enables asymmetric induction, leading to the formation of optically active compounds with high enantiomeric ratios.
Article
Chemistry, Organic
Meng Li, Dong-Hui Wang
Summary: A copper-catalyzed method for synthesizing ortho-aminoazulenols by reacting 2-azulenols with O-benzoylhydroxylamines has been reported, with a wide range of functional groups on amines being compatible. Further synthetic elaboration using 3-amino-2-azulenols as starting materials has been demonstrated.
Article
Chemistry, Organic
Chao Liu, Xiangwen Tan, Jinhui Zhang, Jiahao Wu, Wanqing Wu, Huanfeng Jiang
Summary: This article describes a palladium (II)-catalyzed Nu/Nu'-type 1,1-oxamidation and 1,1-diamination reaction of unactivated alkenyl carbonyl compounds followed by amination. The reaction features a lack of a directing group, good functional group tolerance, and easily operational catalytic reaction conditions. Mechanistic investigations suggest a unique route involving two consecutive nucleopalladations for this 1,1-difunctionalization.
Article
Chemistry, Multidisciplinary
Dayou Zhong, Lin-Yang Wu, Xing-Zhen Wang, Wen-Bo Liu
Summary: A redox-neutral Fe-catalyzed intramolecular C-H amidation of N-benzoyloxyureas was developed, utilizing a simple iron complex generated in situ from Fe(OTf)(2) and bipyridine as the catalyst, and N-benzoyloxyureas as the nitrene precursors without the need for external oxidants. The methodology allowed for the synthesis of a variety of cyclic ureas via aliphatic C(sp(3))-H amidation with excellent yields, and was also applicable to aryl C(sp(2))-H nitrene insertion to provide benzimidazolones in moderate yields.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Physical
Laura Talavera, Robert R. A. Freund, Huihui Zhang, Matthew Wakeling, Mara Jensen, Ruben Martin
Summary: Here, a novel Ni-catalyzed 1,1-difunctionalization of unactivated terminal alkenes is disclosed, allowing for the incorporation of two different heteroatom motifs across an olefin backbone. This streamlines the access to alpha-aminoboronic acid derivatives from simple precursors, and the method exhibits simplicity and generality across a wide range of coupling counterparts.
Article
Chemistry, Physical
Laura Talavera, Robert R. A. Freund, Huihui Zhang, Matthew Wakeling, Mara Jensen, Ruben Martin
Summary: In this study, a novel Ni-catalyzed 1,1-difunctionalization reaction of unactivated terminal alkenes is disclosed, allowing for the incorporation of two different heteroatom motifs across an olefin backbone. This method provides a streamlined approach to the synthesis of alpha-aminoboronic acid derivatives from simple precursors and exhibits simplicity and generality across a wide range of coupling counterparts.
Article
Chemistry, Organic
Hiroto Takahashi, Yuki Nagashima, Ken Tanaka
Summary: The electron-deficient bis(ethoxycarbonyl)-substituted cyclopentadienyl (Cp-E) rhodium(III) complex catalyzes the oxidative intramolecular 1,1-oxyamination of alkenes with N-benzoyl amino acids to produce oxazoloisoindole-2,5-diones. Experimental and theoretical mechanistic studies showed that this oxidative 1,1-oxyamination does not proceed through the aza-Wacker reaction, but involves the formation of a rhoda(III)oxazolidine initiated by carboxylic acid-directed N-H bond cleavage.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Kentaro Yamakawa, Kana Sakamoto, Takahiro Nishimura
Summary: The enantioselective addition of an imide N-H bond to alkenes has been achieved using a cationic iridium catalyst. Bulky diphosphine ligands were crucial for the reaction, and various substrates including styrene derivatives, allylsilanes, and norbornene gave chiral adducts with high enantioselectivity.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Kentaro Yamakawa, Kana Sakamoto, Takahiro Nishimura
Summary: In this study, enantioselective addition of an imide N-H bond to alkenes was achieved using a cationic iridium catalyst. Bulky diphosphine ligands played a crucial role in the reaction. Various substrates, such as styrene derivatives, allylsilanes, and norbornene, reacted well with alkenes to afford chiral adducts with high enantioselectivity.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Mingda Li, Yangbin Jin, Yupeng Chen, Wanqing Wu, Huanfeng Jiang
Summary: This paper reports a new catalytic system for the efficient oxidative amination of unactivated olefins with primary aliphatic amines, leading to the formation of secondary allylic amines. The reaction proceeds through allylic C(sp3)-H activation and nucleophilic amination. The utility of this method is demonstrated in the late-stage modification and streamlined synthesis of drug molecules.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Guoxiang Zhang, Hui He, Xiaoxiao Chen, Shao-Fei Ni, Rong Zeng
Summary: The traditional photoinduced anti-Markovnikov hydroamination of olefins requires high oxidative ability photocatalysts to initiate the single-electron process. However, in this study, we used an inexpensive reagent, bis(2,4,6-triisopropylphenyl) disulfide, with relatively low oxidative ability, as a photo and hydrogen atom transfer catalyst to achieve intramolecular hydroamination. The mechanistic studies and DFT calculations support a novel process involving N centered radical generation through the homolysis of the in situ formed N-S species, followed by cyclization. Various nitrogen-containing cycles can be obtained.
Article
Chemistry, Organic
Wanqiao Huang, Cong Xu, Jianxin Yu, Mang Wang
Summary: An effective method for the aminotrifluoromethylation of alkenes was developed by using PhICF3Cl and ZnI2 as catalysts. The mechanism studies showed that the reaction involves an iodine anion-catalyzed radical chlorotrifluoromethylation of alkenes and a Lewis acid-promoted aminocyclization of the resulting chlorotrifluoromethylated intermediates.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
