TY - JOUR
T1 - A Multifaceted Directing Group Switching Ynones as Michael Donors in Chemo-, Enantio-, and γ-Selective 1,4-Conjugate Additions with Nitroolefins
AU - Liu, Weiwei
AU - Zou, Liwei
AU - Fu, Binbin
AU - Wang, Xinran
AU - Wang, Ke
AU - Sun, Zhongwen
AU - Peng, Fangzhi
AU - Wang, Wei
AU - Shao, Zhihui
N1 - Funding Information:
This work was financially supported by the NSFC (21372193, 21362040), the Program for Changjiang Scholars and Innovative Research Team in University (IRT13095), the Doctoral Fund of Ministry of Education of China (20135301110002), and the Government of Yunnan Province (2013FA026). This paper is dedicated to Professor Barry M. Trost on the occasion of his 75th birthday.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/9/16
Y1 - 2016/9/16
N2 - α,β-Unsaturated ynones have historically been used as Michael acceptors in conjugate addition reactions. Herein, we have demonstrated for the first time that ynones can be harnessed as Michael donors for use in catalytic asymmetric conjugate addition reactions by strategically introducing a CO2t-Bu group as a multitasking directing group. Furthermore, this concept has enabled designer ynones as versatile synthetic equivalents of both α′ anions of ynones and γ monoanions of 1,3-diketones, which are synthetically valued but difficult to generate. The first catalytic enantioselective conjugate addition of ynones as Michael donors has been realized in good yields with high enantioselectivities. A unified approach to regiospecifically and chemo- and enantioselectively access hitherto elusive γ-Michael adducts of 1,3-diketones has been achieved in a divergent manner. The strategy described here by exploring new reactivity and creating new reagents holds great potential applications in other still unsolved transformations.
AB - α,β-Unsaturated ynones have historically been used as Michael acceptors in conjugate addition reactions. Herein, we have demonstrated for the first time that ynones can be harnessed as Michael donors for use in catalytic asymmetric conjugate addition reactions by strategically introducing a CO2t-Bu group as a multitasking directing group. Furthermore, this concept has enabled designer ynones as versatile synthetic equivalents of both α′ anions of ynones and γ monoanions of 1,3-diketones, which are synthetically valued but difficult to generate. The first catalytic enantioselective conjugate addition of ynones as Michael donors has been realized in good yields with high enantioselectivities. A unified approach to regiospecifically and chemo- and enantioselectively access hitherto elusive γ-Michael adducts of 1,3-diketones has been achieved in a divergent manner. The strategy described here by exploring new reactivity and creating new reagents holds great potential applications in other still unsolved transformations.
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U2 - 10.1021/acs.joc.6b01425
DO - 10.1021/acs.joc.6b01425
M3 - Article
AN - SCOPUS:84988504364
SN - 0022-3263
VL - 81
SP - 8296
EP - 8305
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 18
ER -