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J.Am.Chem.Soc.2017,139,2196~2199线型二烯醇硅醚与亚胺的Mannich型反应以γ加成为主,而线型二烯醇金属络合物和亚胺的Mannich型反应往往以α加成的方式进行,这源于线型二烯醇金属络合物γ位的亲核性弱于α位的亲核性.中国科学院上海有机化学研究所殷亮课题组通过大位阻的底物结合大位阻的一价铜-双膦络合物的策略,成功实现了线型二烯醇金属络合物
J. Am. Chem. Soc. 2017, 139, 2196-2199 Mannich-type reaction of linear dienolylsiloxane with imine is dominated by gamma addition whereas linear dienol metal complexes and Mannich imines Type reaction is often carried out in the form of α addition due to the nucleophilicity weaker than α in the γ position of the linear dienol metal complex. The sterically hindered substrate combined with the steric monovalent copper-bisphosphine complex strategy successfully achieved the linear dienolide metal complex