Asymmetric synthesis of propargylic alcohols via aldol reaction of aldehydes with ynals promoted by prolinol ether-transition metal-Bronsted acid cooperative catalysis

作者：Gomez Bengoa Enrique; Garcia Jesus M; Jimenez Sandra; Lapuerta Irati; Mielgo Antonia; Odriozola Jose M; Otazo Itziar; Razkin Jesus; Urruzuno Inaki; Vera Silvia; Oiarbide Mikel; Palomo Claudio^*

来源：Chemical Science, 2013, 4(8): 3198-3204.

DOI：10.1039/c3sc51027a

A catalytic and highly stereoselective entry to propargylic alcohols and products derived thereof is reported based on an unprecedented cross-aldol coupling between unmodified aldehydes and ynals. The method requires an amine-metal salt-Bronsted acid ternary catalyst system and implies synergistic activation of the donor aldehyde via enamine and of the acceptor carbonyl via unique and reversible metal-alkyne complexation. Specifically, by using a combined alpha,alpha-dialkylprolinol silyl ether-CuI-PhCO2H catalyst system, remarkably high levels of diastereo- and enantioselectivity (anti/syn up to %26gt;20 : 1, ee up to %26gt;99%) are achieved.

• 出版日期2013