Highly Stereoselective Synthesis and Hydrogenation of (Z)-1-Alkyl-2-arylvinyl Acetates: a Wide Scope Procedure for the Preparation of Chiral Homobenzylic Esters

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• 作者：Pedro J. González-Liste ; Félix León ; Inmaculada Arribas ; Miguel Rubio ; Sergio E. García-Garrido ; Victorio Cadierno ; Antonio Pizzano
• 刊名：ACS Catalysis
• 出版年：2016
• 出版时间：May 6, 2016
• 年：2016
• 卷：6
• 期：5
• 页码：3056-3060
• 全文大小：349K
• 年卷期：0
• ISSN：2155-5435

文摘

A synthesis of (Z)-1-alkyl-2-arylvinyl acetates 3 with broad scope is reported by using two complementary methods. The first one uses a stereospecific gold-catalyzed addition of acetic acid to 1-iodo-alkynes, followed by a Suzuki coupling. By the second, 1-methyl-2-arylvinyl substrates have been obtained selectively as the Z isomers by O-acylation of enolates of methyl benzyl ketones. In addition, the asymmetric hydrogenation of enol esters 3 has been covered for the first time. Using rhodium catalysts based on chiral phosphine-phosphite ligands (P-OP), highly enantioselective hydrogenations (up to 99% ee) have been achieved for a wide range of substrates. Thus, the synthesis and enantioselective hydrogenation of 3 provides a convenient and versatile procedure for the synthesis of valuable chiral homobenzylic esters.