立体选择性交叉偶联的二级有机三氟硼酸盐：钾 1-（苄氧基）烷基三氟硼酸盐。
Stereospecific cross-coupling of secondary organotrifluoroborates: potassium 1-(benzyloxy)alkyltrifluoroborates.
机构信息
Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
出版信息
J Am Chem Soc. 2012 Oct 10;134(40):16856-68. doi: 10.1021/ja307861n. Epub 2012 Oct 1.
Abstract
Potassium 1-(alkoxy/acyloxy)alkyltrifluoroborates have been synthesized through a copper-catalyzed diboration of aldehydes and subsequent conversion of the resulting potassium 1-(hydroxy)alkyltrifluoroborates. The palladium-catalyzed Suzuki-Miyaura reaction employing the potassium 1-(benzyloxy)alkyltrifluoroborates with aryl and heteroaryl chlorides provides access to protected secondary alcohols in high yields. The β-hydride elimination pathway is avoided through use of the benzyl protecting group, which is proposed to stabilize the diorganopalladium intermediate by coordination of the arene to the metal center. This cross-coupling is stereospecific with complete retention of stereochemistry.
摘要
通过醛的铜催化二硼化反应以及随后将生成的钾 1-(羟基)烷基三氟硼酸盐转化，合成了钾 1-(烷氧基/酰氧基)烷基三氟硼酸盐。使用钯催化的 Suzuki-Miyaura 反应，使钾 1-(苄氧基)烷基三氟硼酸盐与芳基和杂芳基氯化物反应，可以高产率得到保护的仲醇。通过使用苄基保护基来避免β-氢消除途径，该保护基通过芳环与金属中心的配位来稳定二有机钯中间体。该交叉偶联具有立体特异性，立体化学完全保留。
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