Article
Chemistry, Physical
Chunming Gui, Yuanyuan Peng, Yang Zhou, Yixuan Zheng, Haifeng Wang, Qiongjiao Yan, Hui Zhou, Wei Wang, Fen-Er Chen
Summary: This paper reports the copper-catalyzed asymmetric propargylic substitution reaction, which efficiently synthesizes multifunctionalized products bearing a terminal alkyne unit with good stereoselectivity. The products can also be easily derivatized into other potentially valuable organic compounds, showing great potential for pharmaceutical development.
Article
Chemistry, Multidisciplinary
Zhiheng Li, Danran Li, Huaming Xiang, Jian Huang, Yinuo Zheng, Cuiju Zhu, Xiuling Cui, Chao Pi, Hao Xu
Summary: In this study, a highly enantioselective propargylic substitution reaction of anthrones with propargylic esters using copper salts with chiral N, N, P-ligand was disclosed. This strategy shows broad substrate compatibility, mild reaction conditions, excellent yields with remarkable enantioselectivity, and enables the synthesis of diverse products.
CHINESE CHEMICAL LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Hiroaki Tsuji, Yuka Shimizu, Yusuke Miyazaki, Motoi Kawatsura
Summary: The study describes the development of nickel-catalyzed highly enantioselective propargylic amination, which resulted in the successful synthesis of chiral propargylic amines.
Article
Chemistry, Physical
Ni Xiong, Yang Li, Rong Zeng
Summary: We present a dual catalytic strategy for the functionalization of aliphatic carboxylic acids using photoinduced iron/copper catalysts. The photoinduced ligand-to-iron charge transfer process generates an unstabilized alkyl radical, which is then utilized by the copper catalyst for coupling reactions to form C-N or C-C bonds. This system enables efficient conversion of a wide range of aliphatic carboxylic acids and has potential applications in drug discovery.
Article
Chemistry, Physical
Ni Xiong, Yang Li, Rong Zeng
Summary: We have developed a photoinduced iron/copper dual-catalytic strategy for the radical decarboxylation functionalization of aliphatic carboxylic acids. By merging iron-catalyzed decarboxylation with copper catalysis, this system allows efficient conversion of a wide range of aliphatic carboxylic acids for various reactions. The strategy has applications in compound library synthesis and the discovery of pharmaceutical agents.
Article
Chemistry, Multidisciplinary
Ling Dai, Ying-Ying Chen, Li-Jun Xiao, Qi-Lin Zhou
Summary: Intramolecular enantioselective radical C(sp(3))-H functionalization allows for the synthesis of chiral amines, but methods for intermolecular enantioselective C(sp(3))-H amination remain elusive. Here, a cationic copper catalytic system for intermolecular enantioselective benzylic C(sp(3))-H amination with peroxide as an oxidant is reported. This method allows for the transformation of various alkylarenes and amides into chiral amines with high enantioselectivities and has good functional group tolerance and broad substrate scope. Moreover, it can be used to synthesize bioactive molecules, including chiral drugs.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jin-Tao Xia, Ling Li, Xiang-Ping Hu
Summary: A copper-catalyzed asymmetric decarboxylative propargylic alkylation has been successfully achieved, allowing for the highly stereoselective formation of acyclic vicinal tri- and tetrasubstituted stereocenters. This strategy has demonstrated high potential in resolving challenges present in traditional catalytic propargylic alkylation by preparing optically active quaternary alpha-amino acid esters with chiral tertiary propargylic moieties in high yields and good to excellent diastereo- and enantioselectivities.
Article
Chemistry, Multidisciplinary
Jingjing Wu, Chao Shu, Zhihang Li, Adam Noble, Varinder K. Aggarwal
Summary: This article describes a visible-light photoredox-catalyzed decarboxylative halogenation reaction using inexpensive inorganic halide salts as halogenating agents. Bromination with lithium bromide can be achieved using an organic photoredox catalyst under simple conditions, while chlorination requires dual photoredox-copper catalysis. The reaction exhibits excellent functional group tolerance and can convert structurally complex natural products into alkyl bromides and chlorides. Additionally, the method is also applicable to thiocyanation reactions with potassium thiocyanide for the synthesis of alkyl thiocyanates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Jian Huang, Han-Han Kong, Si-Jia Li, Rui-Jin Zhang, Hao-Dong Qian, Dan-Ran Li, Jin-Yu He, Yi-Nuo Zheng, Hao Xu
Summary: The highly enantioselective copper-catalyzed propargylic amination of propargylic esters with amine hydrochloride salts using chiral N,N,P-ligands has been successfully developed. This method demonstrates a broad substrate scope and wide functional group tolerance, producing propargylic amines in good to excellent yields with high enantioselectivities (up to 99% ee). The approach was further validated by late-stage functionalization of marketed pharmaceuticals.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ken Sakata, Yuuri Uehara, Shiona Kohara, Takeshi Yoshikawa, Yoshiaki Nishibayashi
Summary: In this study, the effects of propargylic substituents on the enantioselectivity and reactivity in propargylic substitution reactions were further investigated using density functional theory calculations. The results showed that substitution of a methyl group at the propargylic position could reverse the stereoselectivity, while substitution of a trifluoromethyl group for a methyl group was suggested to enhance the enantioselectivity.
Article
Chemistry, Physical
Changhua Song, Hong-Hao Zhang, Shouyun Yu
Summary: In this study, a decarboxylative allylic benzylation catalyzed by Pd/photoredox in a regio- and enantioselective manner is achieved. This method uses readily available aryl acetic acids as benzylic nucleophile equivalents without preactivation. The mild and atom-economical protocol expands the scope of coupling partners of allylic electrophiles. Additionally, vinyl epoxides can undergo this transformation smoothly, producing various chiral homoallylic alcohols bearing all-carbon quaternary stereocenters.
Article
Chemistry, Multidisciplinary
Wei Zhao, Wenji Wang, Huan Zhou, Qishan Liu, Zhiqing Ma, Haizhou Huang, Mingxin Chang
Summary: A one-pot asymmetric hydrogenation of pyridines with subsequent N-alkylation using a traceless Bronsted acid activation strategy is reported. The reaction exhibits high stereoselectivity and can be used to synthesize indolizidines and quinolizidines. Experimental and theoretical studies reveal that chloride anion and noncovalent interactions play important roles in determining the stereoselectivity of the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Hua-Hua Wang, Hui Shao, Guanglong Huang, Jianqiang Fan, Wai-Pong To, Li Dang, Yungen Liu, Chi-Ming Che
Summary: In this study, chiral iron porphyrin complexes were found to catalyze the asymmetric intramolecular C(sp(3))-H amination of aryl and arylsulfonyl azides, providing chiral indolines and benzofused cyclic sulfonamides, respectively. The reactions exhibited high enantioselectivity (up to 93% ee) and high yields (up to 99%) under mild conditions with 410 nm light.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Peng Zhang, Xiao-Mei Wang, Qi Xu, Chang-Qiu Guo, Peng Wang, Chuan-Jun Lu, Ren-Rong Liu
Summary: In this study, a Pd-catalyzed cross-coupling strategy was employed for the synthesis of N-C axially chiral biaryl molecules with excellent enantioselectivities and good yields. The practicality of this reaction was demonstrated in the synthesis of biologically relevant molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Donglei Wang, Ying-Bo Shao, Yunrong Chen, Xiao-Song Xue, Xiaoyu Yang
Summary: An efficient method for the asymmetric synthesis of planar-chiral macrocycles (paracyclophanes) has been developed using chiral phosphoric acid catalysis for enantioselective electrophilic aromatic aminations with azodicarboxylates. This method allows for the synthesis of a wide range of chiral macrocycles with varying ring sizes and functional groups, achieving high yields and enantioselectivities. The mechanism and origins of the stereoselectivities of these reactions were investigated through experimental studies and computational calculations. Preliminary utilization of the planar-chiral macrocycle as a chiral organocatalyst demonstrated the potential applications of these novel chiral skeletons.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
