MIDA(-甲基亚氨基二乙酸)硼酸酯的氧化重排：反应机理与合成应用。
Oxidative Rearrangement of MIDA (-Methyliminodiacetic Acid) Boronates: Mechanistic Insights and Synthetic Applications.
机构信息
Davenport Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON M5S 3H6, Canada.
Chemical Physics Theory Group, Department of Chemistry, University of Toronto, Toronto, ON M5S 3H6, Canada.
出版信息
Org Lett. 2021 Jan 15;23(2):324-328. doi: 10.1021/acs.orglett.0c03823. Epub 2021 Jan 6.
Herein we report that coordinative hemilability allows the MIDA (-methyliminodiacetic acid) nitrogen to behave as a nucleophile and intramolecularly intercept palladium π-allyl intermediates. A mechanistic investigation indicates that this rearrangement proceeds through an S2-like displacement at tetrasubstituted boron to furnish novel DABN boronates. Oxidative addition into the N-C bond of the DABN scaffold furnishes borylated π-allyl intermediates that can then be trapped with a variety of nucleophiles, including in a three-component coupling.
在此，我们报告称，配位的半配位能力使 MIDA（-甲基亚氨基二乙酸）氮原子表现为亲核试剂，并在分子内捕获钯π-烯丙基中间体。一项机理研究表明，这种重排通过在四取代硼原子上进行 S2 类似的取代反应进行，生成新型的 DABN 硼酸酯。氧化加成到 DABN 骨架的 N-C 键中生成硼化的 π-烯丙基中间体，然后可以用各种亲核试剂捕获，包括在三组分偶联中。
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