Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta-cho Midori-ku, Yokohama, 226-8503, Japan.
School of Life Science and Technology, Tokyo Institute of Technology, 4259 Nagatsuta-cho Midori-ku, Yokohama, 226-8503, Japan.
Angew Chem Int Ed Engl. 2022 Feb 7;61(7):e202113558. doi: 10.1002/anie.202113558. Epub 2021 Dec 29.
A palladium-catalyzed N-H/B-H double activation of 1,2-dihydro-1,2-benzazaborines proceeded via cycloaddition with vinyl ethylene carbonate to produce polycyclic oxazaborolidines in 31-96 % yield. The key step in this process is the release of molecular hydrogen from a borate intermediate. Using a SPINOL-derived phosphoramidite as a chiral ligand, chiral oxazaborolidines were synthesized in good to high yields with excellent enantioselectivity (up to 95 % ee). The vinyl group of the resulting oxazaborolidine underwent metathesis, Heck reaction, and Wacker oxidation without affecting the oxazaborolidine framework.
钯催化的 1,2-二氢-1,2-苯并氮杂硼烷的 N-H/B-H 双重活化，通过与乙烯碳酸亚乙酯的环加成反应，以 31-96%的产率生成多环恶唑硼烷。该过程中的关键步骤是硼酸酯中间体释放分子氢。使用 SPINOL 衍生的手性磷酰胺作为手性配体，以良好到高产率（高达 95%ee）合成了手性恶唑硼烷。所得恶唑硼烷的乙烯基通过复分解、Heck 反应和 Wacker 氧化反应进行反应，而不影响恶唑硼烷骨架。
