CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan 430079, China.
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, People's Republic of China.
J Am Chem Soc. 2021 Mar 24;143(11):4168-4173. doi: 10.1021/jacs.1c01260. Epub 2021 Mar 11.
1,3-Dienes are readily available feedstocks that are widely used in the laboratory and industry. However, the potential of converting 1,3-dienes into value-added products, especially chiral products, has not yet been fully exploited. By synergetic photoredox/copper catalysis, we achieve the first visible-light-induced, enantioselective carbocyanation of 1,3-dienes by using carboxylic acid derivatives and trimethylsilyl cyanide. Under mild and neutral conditions, a diverse range of chiral allyl cyanides are produced in generally good efficiency and with high enantioselectivity from bench-stable and user-safe chemicals. Moreover, preliminary results also confirm that this success can be expanded to 1,3-enynes and the four-component carbonylative carbocyanation of 1,3-dienes and 1,3-enynes.
1,3-二烯是一种易得的原料，广泛应用于实验室和工业领域。然而，将 1,3-二烯转化为附加值产品，特别是手性产品的潜力尚未得到充分开发。通过协同光氧化还原/铜催化，我们实现了首例可见光诱导、对映选择性的 1,3-二烯的羧基衍生物和三甲基硅基氰化物的碳氰化反应。在温和中性条件下，使用稳定且用户安全的化学试剂，从大量的手性烯丙基氰化物中以较高的效率和对映选择性得到了广泛的产物。此外，初步结果还证实，这一成功可以扩展到 1,3-烯炔和 1,3-二烯和 1,3-烯炔的四组分羰基化碳氰化反应。
