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Chirality memory of α-methylene-π-allyl iridium species

Yifan Cui, Yizhan Zhai, Junzhe Xiao, Can Li, Wei‐Feng Zheng, Chaofan Huang, Guolin Wu, Anni Qin, Jie Lin, Qi Liu, Huanan Wang, Penglin Wu, Haibo Xu, Yangguangyan Zheng, Shengming Ma

2021Chemical Science16 citationsDOIOpen Access PDF

Abstract

an optically active alkylidene-π-allyl iridium intermediate, leading to a highly stereoselective electrophilic allenylation with amines. Specifically, we have established the transition metal-mediated highly stereoselective 2,3-allenylation of amines by using optically active 2,3-allenyl carbonates under the catalysis of a nonchiral iridium(iii) complex. This method is compatible with sterically bulky and small substituents on both amines and 2,3-allenyl carbonates and furnishes the desired optically active products with a high efficiency of chirality transfer. Further mechanistic experiments reveal that the isomerization of the optically active alkylidene-π-allyl iridium intermediate is very slow.

Topics & Concepts

Chirality (physics)ElectrophileSteric effectsIridiumAxial chiralityChemistryIsomerizationStereoselectivityMethylenePlanar chiralityStereochemistryPhotochemistryCatalysisEnantioselective synthesisPhysicsOrganic chemistryParticle physicsChiral symmetry breakingNambu–Jona-Lasinio modelQuarkAxial and Atropisomeric Chirality SynthesisAsymmetric Synthesis and CatalysisCatalytic C–H Functionalization Methods
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