Chiral Iron Porphyrins Catalyze Enantioselective Intramolecular C(sp(3))-H Bond Amination Upon Visible-Light Irradiation

Wang, Hua-Hua1; Shao, Hui1; Huang, Guanglong6,7,8; Fan, Jianqiang1; To, Wai-Pong2,3; Dang, Li6,7,8; Liu, Yungen1; Che, Chi-Ming1,2,3,4,5

2023-02-01

10.1002/anie.202218577

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

Iron-catalyzed asymmetric amination of C(sp(3))-H bonds is appealing for synthetic applications due to the biocompatibility and high earth abundance of iron, but examples of such reactions are sparse. Herein we describe chiral iron complexes of meso- and beta-substituted-porphyrins that can catalyze asymmetric intramolecular C(sp(3))-H amination of aryl and arylsulfonyl azides to afford chiral indolines (29 examples) and benzofused cyclic sulfonamides (17 examples), respectively, with up to 93 % ee (yield: up to 99 %) using 410 nm light under mild conditions. Mechanistic studies, including DFT calculations, for the reactions of arylsulfonyl azides reveal that the Fe(NSO2Ar) intermediate generated in situ under photochemical conditions reacts with the C(sp(3))-H bond through a stepwise hydrogen atom transfer/radical rebound mechanism, with enantioselectivity arising from cooperative noncovalent interactions between the Fe(NSO2Ar) unit and the peripheral substituents of the chiral porphyrin scaffold.

Amination Asymmetric Catalysis Iron Photocatalysis Porphyrins

SCI ; EI

英语

NI论文

第一 ; 通讯

National Natural Science Foundation of China["NSFC 21871127","91856203"] ; Shenzhen Science and Technology Innovation Commission[JCYJ20190809141203613] ; General Research Fund from the Hong Kong Research Grants Council["17301817","17304019"]

Chemistry

Chemistry, Multidisciplinary

WOS:000937297300001

WILEY-V C H VERLAG GMBH

20230713598871

Amides ; Amines ; Atoms ; Catalysis ; Enantioselectivity ; Free radical reactions ; Ions ; Iron compounds ; Photochemical reactions ; Porphyrins ; Reaction intermediates ; Scaffolds

Construction Equipment:405.1 ; Light/Optics:741.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Atomic and Molecular Physics:931.3

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
2.Univ Hong Kong, State Key Lab Synthet Chem, Hong Kong, Peoples R China
3.Univ Hong Kong, Dept Chem, Hong Kong, Peoples R China
4.HKU Shenzhen Inst Res & Innovat, Shenzhen 518057, Guangdong, Peoples R China
5.Hong Kong Sci & Technol Pk, Lab Synthet Chem & Chem Biol Ltd, New Terr, Units 1503 1511,15-F,Bldg 17 W, Hong Kong, Peoples R China
6.Shantou Univ, Dept Chem, Shantou 515063, Guangdong, Peoples R China
7.Shantou Univ, Key Lab Preparat & Applicat Ordered Struct Mat Gua, Shantou 515063, Guangdong, Peoples R China
8.Chem & Chem Engn Guangdong Lab, Shantou 515063, Guangdong, Peoples R China

Wang, Hua-Hua,Shao, Hui,Huang, Guanglong,et al. Chiral Iron Porphyrins Catalyze Enantioselective Intramolecular C(sp(3))-H Bond Amination Upon Visible-Light Irradiation[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2023,62.

Wang, Hua-Hua.,Shao, Hui.,Huang, Guanglong.,Fan, Jianqiang.,To, Wai-Pong.,...&Che, Chi-Ming.(2023).Chiral Iron Porphyrins Catalyze Enantioselective Intramolecular C(sp(3))-H Bond Amination Upon Visible-Light Irradiation.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,62.

Wang, Hua-Hua,et al."Chiral Iron Porphyrins Catalyze Enantioselective Intramolecular C(sp(3))-H Bond Amination Upon Visible-Light Irradiation".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 62(2023).