1207538-89-3Relevant academic research and scientific papers
Catalytic Asymmetric Allylic Substitution with Copper(I) Homoenolates Generated from Cyclopropanols
Shi, Chang-Yun,Yin, Liang,Zhang, Qi,Zhou, Si-Wei
, p. 26351 - 26356 (2021/11/09)
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.
First enantiocontrolled formal synthesis of (+)-neovibsanin B, A neurotrophic diterpenoid
Esumi, Tomoyuki,Mori, Takehiro,Zhao, Ming,Toyota, Masao,Fukuyama, Yoshiyasu
supporting information; experimental part, p. 888 - 891 (2010/04/29)
(Figure Presented) An enantiocontrolled formal synthesis of (+)-neovibsanin B has been achieved by a sequence that applies an asymmetric 1,4-addition of (H2C=CH)2Cu(CN)Li2 to trisubstituted α,β-carboxylic acid derivative 1 to induce the chirality at the C-11 all-carbon quaternary center. Together with a modified Negishi cyclic carbopalladation-carbonylative esterification tandem reaction for constructing the A-ring, the synthesis was completed.
