Stereoselective Vinylic C-H Addition via Metallaphotoredox Migration

被引:0
作者
Ding, Linlin [1 ]
Wang, Minyan [1 ]
Liu, Yiming [4 ]
Lu, Hongjian [1 ]
Zhao, Yue [1 ]
Shi, Zhuangzhi [1 ,2 ,3 ]
机构
[1] Nanjing Univ, Chem & Biomed Innovat Ctr ChemB, Sch Chem & Chem Engn, State Key Lab Coordinat Chem, Nanjing 210093, Peoples R China
[2] Nanjing Normal Univ, Sch Chem & Mat Sci, Nanjing 210023, Peoples R China
[3] Henan Normal Univ, Sch Chem & Chem Engn, Xinxiang 453007, Peoples R China
[4] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA
基金
国家重点研发计划; 中国国家自然科学基金;
关键词
allylic alcohols; enantioselectivity; metallaphotoredox; nickel catalysis; DFT calculations; DNA-POLYMERASE-BETA; ALLYLIC ALCOHOLS; TRANSITION-METAL; SUBSTITUTION; ARYLATION; ARYL; (+)-MYRISTININ-A; SCOPE; BOND;
D O I
10.1002/anie.202413557
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Geometrically defined allylic alcohols with SE, SZ, RE and RZ stereoisomers serve as valuable intermediates in synthetic chemistry, attributed to the stereoselective transformations enabled by the alkenyl and hydroxyl functionalities. When an ideal scenario presents itself with four distinct stereoisomers as potential products, the simultaneous control vicinal stereochemistry in a single step would offer a direct pathway to any desired stereoisomer. Here, we unveil a metallaphotoredox migration strategy to access stereodefined allylic alcohols through vinylic C-H activation with aldehydes. This method harnesses a chiral nickel catalyst in concert with a photocatalyst to enable a 1,4-Ni migration by using readily accessible 2-vinyl iodoarenes as starting materials. The efficacy of this methodology is highlighted by the precise construction of all stereoisomers of allylic alcohols bearing analogous substituents and the efficient synthesis of key intermediates en route to Myristinin family. Experimental and computational studies have shed light on pivotal aspects including the synergy of metal catalysis and photocatalysis, the driving forces behind the migration, and the determination of absolute configuration in the C-H addition process.
引用
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页数:11
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共 56 条
[1]   Hydroxy group directivity in the epoxidation of chiral allylic alcohols: Control of diastereoselectivity through allylic strain and hydrogen bonding [J].
Adam, W ;
Wirth, T .
ACCOUNTS OF CHEMICAL RESEARCH, 1999, 32 (08) :703-710
[2]   Rapid Access to 2,2-Disubstituted Indolines via Dearomative Indolic-Claisen Rearrangement: Concise, Enantioselective Total Synthesis of (+)-Hinckdentine A [J].
Baidilov, Daler ;
Elkin, Pavel K. ;
Athe, Sudhakar ;
Rawal, Viresh H. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2023, 145 (27) :14831-14838
[4]   Photocatalytic Late-Stage C-H Functionalization [J].
Bellotti, Peter ;
Huang, Huan-Ming ;
Faber, Teresa ;
Glorius, Frank .
CHEMICAL REVIEWS, 2023, 123 (08) :4237-4352
[5]   A highly enantioselective catalyst for the asymmetric Nozaki-Hiyama-Kishi reaction of allylic and vinylic halides [J].
Berkessel, A ;
Menche, D ;
Sklorz, CA ;
Schröder, M ;
Paterson, I .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (09) :1032-+
[6]   Transition metal-catalyzed allylic substitution reactions with unactivated allylic substrates [J].
Butt, Nicholas A. ;
Zhang, Wanbin .
CHEMICAL SOCIETY REVIEWS, 2015, 44 (22) :7929-7967
[7]   Design, synthesis, and carbon-heteroatom coupling reactions of organometallic nickel(IV) complexes [J].
Camasso, Nicole M. ;
Sanford, Melanie S. .
SCIENCE, 2015, 347 (6227) :1218-1220
[8]   Metallaphotoredox: The Merger of Photoredox and Transition Metal Catalysis [J].
Chan, Amy Y. ;
Perry, Ian B. ;
Bissonnette, Noah B. ;
Buksh, Benito F. ;
Edwards, Grant A. ;
Frye, Lucas, I ;
Garry, Olivia L. ;
Lavagnino, Marissa N. ;
Li, Beryl X. ;
Liang, Yufan ;
Mao, Edna ;
Millet, Agustin ;
Oakley, James, V ;
Reed, Nicholas L. ;
Sakai, Holt A. ;
Seath, Ciaran P. ;
MacMillan, David W. C. .
CHEMICAL REVIEWS, 2022, 122 (02) :1485-1542
[9]   Alcohol-alcohol cross-coupling enabled by SH2 radical sorting [J].
Chen, Ruizhe ;
Intermaggio, Nicholas E. ;
Xie, Jiaxin ;
Rossi-Ashton, James A. ;
Gould, Colin A. ;
Martin, Robert T. ;
Alcazar, Jesus ;
MacMillan, David W. C. .
SCIENCE, 2024, 383 (6689) :1350-1357
[10]   (+)-myristinins A and D from Knema elegans, which inhibit DNA polymerase β and cleave DNA [J].
Deng, JZ ;
Starck, SR ;
Li, SS ;
Hecht, SM .
JOURNAL OF NATURAL PRODUCTS, 2005, 68 (11) :1625-1628