Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 50, Pages 26351-26356Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202110709
Keywords
allylic substitution; asymmetric catalysis; copper catalyst; cyclopropanols; homoenolates
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Funding
- National Natural Science Foundation of China [21871287, 21922114]
- Science and Technology Commission of Shanghai Municipality [20JC1417100, 21XD1424800]
- CAS Key Laboratory of Synthetic Chemistry of Natural Substances and Shanghai Institute of Organic Chemistry
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A catalytic asymmetric allylic substitution using copper(I) homoenolates as nucleophiles has been achieved, with high yields and enantioselectivity. The method is applicable to a broad range of substrates and can be extended to the construction of chiral quaternary carbon centers.
By using copper(I) homoenolates as nucleophiles, which are generated through the ring-opening of 1-substituted cyclopropane-1-ols, a catalytic asymmetric allylic substitution with allyl phosphates is achieved in high to excellent yields with high enantioselectivity. Both 1-substituted cyclopropane-1-ols and allylic phosphates enjoy broad substrate scopes. Remarkably, various functional groups, such as ether, ester, tosylate, imide, alcohol, nitro, and carbamate are well tolerated. Moreover, the present method is nicely extended to the asymmetric construction of quaternary carbon centers. Some control experiments argue against a radical-based reaction mechanism and a catalytic cycle based on a two-electron process is proposed. Finally, the synthetic utilities of the product are showcased by means of the transformations of the terminal olefin group and the ketone group.
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