通过催化烯基到烯丙基 1,4-铑（I）迁移实现酮与 1,3-烯炔的芳基化分子内烯丙基化反应。
Arylative Intramolecular Allylation of Ketones with 1,3-Enynes Enabled by Catalytic Alkenyl-to-Allyl 1,4-Rhodium(I) Migration.
机构信息
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, UK.
出版信息
Angew Chem Int Ed Engl. 2017 Jun 12;56(25):7227-7232. doi: 10.1002/anie.201703155. Epub 2017 May 19.
Alkenyl-to-allyl 1,4-rhodium(I) migration enables the generation of nucleophilic allylrhodium(I) species by remote C-H activation. This new mode of reactivity was employed in the diastereoselective reaction of arylboron reagents with substrates containing a 1,3-enyne tethered to a ketone, to give products containing three contiguous stereocenters. The products can be obtained in high enantioselectivities using a chiral sulfur-alkene ligand.
烯基到烯丙基 1,4-铑（I）迁移通过远程 C-H 活化生成亲核烯丙基铑（I）物种。这种新的反应模式被用于含酮的 1,3-炔基桥联底物与芳基硼试剂的非对映选择性反应，得到含有三个连续立体中心的产物。使用手性硫-烯配体可以获得高对映选择性的产物。
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