Palladium-catalyzed regio- and enantioselective migratory allylic C(sp3)-H functionalization

被引:41
作者
Chen, Ye-Wei [1 ,2 ]
Liu, Yang [1 ]
Lu, Han-Yu [1 ,2 ]
Lin, Guo-Qiang [1 ,2 ]
He, Zhi-Tao [1 ]
机构
[1] Univ Chinese Acad Sci, Shanghai Inst Organ Chem, Ctr Excellence Mol Synth, CAS Key Lab Synthet Chem Nat Subst, Shanghai, Peoples R China
[2] ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai, Peoples R China
基金
中国国家自然科学基金;
关键词
C-H OXIDATION; NONCONJUGATED DIENES; TERMINAL OLEFINS; ASYMMETRIC-SYNTHESIS; WALKING METALS; ARYL IODIDES; HYDROAMINATION; AMINES; ACID; SUBSTITUTION;
D O I
10.1038/s41467-021-25978-6
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Transition metal-catalyzed asymmetric allylic substitution with a suitably pre-stored leaving group in the substrate is widely used in organic synthesis. In contrast, the enantioselective allylic C(sp(3))-H functionalization is more straightforward but far less explored. Here we report a catalytic protocol for the long-standing challenging enantioselective allylic C(sp(3))-H functionalization. Through palladium hydride-catalyzed chain-walking and allylic substitution, allylic C-H functionalization of a wide range of acyclic nonconjugated dienes is achieved in high yields (up to 93% yield), high enantioselectivities (up to 98:2 er), and with 100% atom efficiency. Exploring the reactivity of substrates with varying pK(a) values uncovers a reasonable scope of nucleophiles and potential factors controlling the reaction. A set of efficient downstream transformations to enantiopure skeletons showcase the practical value of the methodology. Mechanistic experiments corroborate the PdH-catalyzed asymmetric migratory allylic substitution process. Alkene isomerizations and asymmetric C-H functionalizations have been independently studied, but their combination in one protocol is uncommon. Here the authors show a palladium-catalyzed method to iteratively "walk" a terminal alkene along a carbon chain to a position next to styrenes where a soft nucleophile is added asymmetrically.
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页数:9
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