Visible-Light-Induced N-Radical Directed Remote Functionalization of sp 3 C-H Bonds

doi:10.6023/A19050183

Acta Chimica Sinica ›› 2019, Vol. 77 ›› Issue (9): 841-849.DOI: 10.6023/A19050183 Previous Articles Next Articles

Special Issue: 有机自由基化学

Review

可见光催化的氮自由基导向远程sp ³碳氢官能团化反应

肖丽^a^*(), 李嘉恒^b, 王挺^b^*()

^aBiogen, 115 Broadway, Cambridge, Massachusetts 02142, United States
^bDepartment of Chemistry, University at Albany, State University of New York, 1400 Washington Avenue, Albany, New York 12222, United States

投稿日期:2019-05-15 发布日期:2019-08-14
通讯作者: 肖丽,王挺 E-mail:xiao.221@buckeyemail.osu.edu;twang3@albany.edu
作者简介:肖丽, 2008~2012年就读于武汉大学化学与分子科学学院; 2012~2017年就读于俄亥俄州立大学化学与生物化学学院有机化学专业(2017年获得博士学位, 导师: Craig Forsyth教授); 2018年至今在美国Biogen生物制药公司从事神经领域药物合成与工艺相关研究工作.|李嘉恒, 1988年出生于吉林省吉林市. 2012年毕业于吉林大学化学学院后在东北师范大学(NENU)王芒教授指导下开展有机氟化学研究, 并于2017年获得理学博士学位. 毕业后就职于吉林大学第一医院表观遗传医药研究所从事新药研发. 2018年8月加入纽约州立大学-奥尔巴尼分校(SUNY-Albany)王挺课题组进行博士后研究, 目前主要围绕新型有机光催化剂的合成及其应用开展相关研究工作.|王挺, 2001~2005年就读于天津大学药物科学与技术学院, 2011年在俄亥俄州立大学获博士学位. 2011至2015年在斯隆-凯特琳癌症研究中心从事博士后工作. 2015年9月加入纽约州立大学-奥尔巴尼分校(SUNY-Albany)化学系. 目前主要研究领域: 有机光催化合成方法学的研究, 以及运用新的光催化方法构建有生物活性的小分子天然产物, 糖类化合物, 多肽和糖肽化合物.

Visible-Light-Induced N-Radical Directed Remote Functionalization of sp ³ C-H Bonds

Xiao, Li^a^*(), Li, Jiaheng^b, Wang, Ting^b^*()

^aBiogen, 115 Broadway, Cambridge, Massachusetts 02142, United States
^bDepartment of Chemistry, University at Albany, State University of New York, 1400 Washington Avenue, Albany, New York 12222, United States

Received:2019-05-15 Published:2019-08-14
Contact: Xiao, Li,Wang, Ting E-mail:xiao.221@buckeyemail.osu.edu;twang3@albany.edu

The selective functionalization of unactivated sp ³ carbon-hydrogen (C—H) bond is an attractive strategy in modern organic transformation. The hydrogen atom transfer (HAT) catalysis has recently shown its advances in remotely selective activation of an inert C—H bond with great functional group compatibility, generating new carbon-carbon (C—C) bonds and carbon-heteroatom (C—O, C—N, C—X) bonds. Therefore, the remote sp ³ C—H functionalization has become an intensively investigated research area, drawing extensive attention in synthetic community. Particularly, the 1,5-hydrogen atom abstraction of nitrogen radicals, the key step of the Hoffman-L?ffler-Freytag (HLF) reaction, has been widely applied in the preparation of heterocycles. Comparing to the well-studied area of nucleophilic N-species, N-centered radical based reactions are still underdeveloped. The limited utility is partially due to the required use of hazardous radical initiators, elevated temperatures, or high-energy UV irradiation for the generation of N-radicals. Recently, visible-light photoredox catalysis has been leading efficient accesses to Nitrogen-radicals under mild conditions. The visible-light-induced nitrogen radical formation has also stimulated the development of the remote sp ³ C—H functionalization by photoredox catalysis. The classic HLF reaction requires pre-functionalization at N-center in the substrate to promote the formation of N-radical. Recently, a direct N—H single electron transfer (SET) oxidation was realized by photoredox catalysis in Knowles and Rovis’s group, generating N-radicals efficiently. The processes significantly simplified the preparation of the HLF reaction substrates and broaden the application of this classic reaction. In addition, the visible-light-induced nitrogen radical-directed reaction on modified imines provided possibilities for the remote sp ³ C—H functionalization of ketones, as ketone is the product of imine hydrolysis. Moreover, the application of chiral Lewis acid catalysis combined with visible-light photoredox catalysis enabled the asymmetric alkylation of the unactivated remote sp ³ C—H position, which achieves both regioselective and stereoselective functionalization. In conclusion, this strategy takes advantage of mild generation of N-radicals upon visible-light excitation. Subsequent 1,5-hydrogen atom transfer (1,5-HAT) and intermolecular radical coupling would realize the remote functionalization of unactivated sp ³ C—H bonds. The strategies have been successfully applied in remote C(sp ³)—H amidation, fluorination, chlorination, iodination, alkylation, vinylation, allylation, oxygenation, thioetherification, cyanation and alkynylation. In this review, we focus on visible-light-induced nitrogen radical directed functionalization of remote sp ³ C—H bonds, summarized the methodologies, and briefly reviewed their synthetic applications in pharmaceuticals and natural products.

Key words: visible-light, radical, remote functionalization

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Xiao, Li, Li, Jiaheng, Wang, Ting. Visible-Light-Induced N-Radical Directed Remote Functionalization of sp ³ C-H Bonds[J]. Acta Chimica Sinica, 2019, 77(9): 841-849.

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Fig. & Tab. 21

Figure 1. Yu group’s remote chlorination

Figure 2. Knowles Group’s blue-light-induced amidyl radical directed remote C—H functionalization

Figure 3. Mechanism of Knowles Group’s amidyl directed remote C—H functionalization

Figure 4. Rovis Group’s amidyl radical directed remote functionalization

Figure 5. Selective substrates of photoredox-catalyzed remote C—H alkylation

Figure 6. Amidyl radical directed remote functionalization through 1,5-HAT and 1,6-HAT

Figure 7. Photoredox-catalyzed alkylation of unactivated sp3 C—H bonds

Figure 8. Asymmetric alkylation of remote C(sp3)—H bonds by dual catalysis

Figure 9. Mechanism of asymmetric alkylation of remote C(sp3)—H bonds by dual catalysis

Figure 10. Nevado group’s C(sp3)—H functionalizations

Figure 11. Transition metal free amidyl radical directed γ-position functionalization

Figure 12. Mechanism of transition metal free amidyl radical directed γ-position functionalization

Figure 13. Remote vinylation of O-acyl oximes

Figure 14. Remote radical C—H functionalization using sulfone reagents

Figure 15. Leonori group’s iminyl radical promoted remote functionalization

Figure 16. Studer group’s iminyl radical promoted remote functionalization

Figure 17. Leonori group’s iminyl radical promoted fluorination, chlorination, thioetherification, cyanation and alkynylation

Figure 18. Nagib group’s C—H iodination

Figure 19. Amidyl radical directed remote allylation and proposed mechanism

Figure 20. Amidyl radical promoted 1,5-hydrogen atom transfer/oxidation cascade

Figure 21. Tambar group’s amidyl radical directed remote C—H allylation

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可见光催化的氮自由基导向远程sp ³碳氢官能团化反应

Visible-Light-Induced N-Radical Directed Remote Functionalization of sp ³ C-H Bonds

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可见光催化的氮自由基导向远程sp 3碳氢官能团化反应