Direct catalytic asymmetric Mannich-type reaction of hydroxyketone using a Et2Zn/linked-BINOL complex: synthesis of either anti- or syn-beta-amino alcohols

Journal of the American Chemical Society
Shigeki MatsunagaMasakatsu Shibasaki

Abstract

Full details of a direct catalytic asymmetric Mannich-type reaction of a hydroxyketone using a Et2Zn/(S,S)-linked-BINOL complex are described. By choosing the proper protective groups on imine nitrogen, either anti- or syn-beta-amino alcohol was obtained in good diastereomeric ratio, yield, and excellent enantiomeric excess using the same zinc catalysis. N-Diphenylphosphinoyl (Dpp) imine 3 gave anti-beta-amino alcohols in anti/syn = up to >98/2, up to >99% yield, and up to >99.5% ee, while Boc-imine 4 gave syn-beta-amino alcohols in anti/syn = up to 5/95, up to >99% yield, and up to >99.5% ee. The high catalyst turnover number (TON) is also noteworthy. Catalyst loading was successfully reduced to 0.02 mol % (TON = up to 4920) for the anti-selective reaction and 0.05 mol % (TON = up to 1760) for the syn-selective reaction. The Et2Zn/(S,S)-linked-BINOL complex exhibited far better TON than in previous reports of catalytic asymmetric Mannich-type reactions. Mechanistic studies to clarify the reason for the high catalyst efficiency as well as transformations of Mannich adducts are also described.

References

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Apr 17, 2003·Journal of the American Chemical Society·Shigeki MatsunagaMasakatsu Shibasaki
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Citations

Jan 26, 2006·Journal of the American Chemical Society·Susumu MitsumoriCarlos F Barbas
May 23, 2007·Journal of the American Chemical Society·Kenneth J Fraunhoffer, M Christina White
Aug 4, 2009·Journal of the American Chemical Society·Grant T Rice, M Christina White
Jun 30, 2006·Organic Letters·Alvaro Salvador GonzalezJuan C Carretero
Mar 1, 2006·Chemical Society Reviews·Masakatsu Shibasaki, Shigeki Matsunaga
Sep 30, 2006·Chemical Communications : Chem Comm·Jun-ichi MatsuoHiroyuki Ishibashi
Mar 16, 2007·Chemical Communications : Chem Comm·Susumu SaitoShū Kobayashi
Jan 16, 2014·The Journal of Organic Chemistry·Yuanzhen XieZhenhua Gu
Mar 10, 2016·Journal of the American Chemical Society·Barry M TrostChao-I Joey Hung
Nov 4, 2015·Organic Letters·Vera M FoleyGerard P McGlacken
Oct 22, 2016·Angewandte Chemie·Jessica Z ChanMasayuki Wasa
May 18, 2017·Chemistry : a European Journal·Nishant Singh, Beatriu Escuder
Sep 8, 2011·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Shigeki Matsunaga, Tatsuhiko Yoshino
Dec 14, 2006·Angewandte Chemie·Jung Woon YangBenjamin List
Sep 28, 2005·Chemistry : a European Journal·Xuenong XuYoshiji Takemoto
Sep 26, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Song SunYingming Yao
Nov 5, 2013·Chemical Society Reviews·Jan Vesely, Ramon Rios
Sep 7, 2019·Angewandte Chemie·Hui Yang, Wen-Hua Zheng

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