导向的、钯(II)催化的烯烃分子间氨羟化反应使用温和的氧化体系。
Directed, Palladium(II)-Catalyzed Intermolecular Aminohydroxylation of Alkenes Using a Mild Oxidation System.
机构信息
Department of Chemistry , The Scripps Research Institute , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States.
Chemical Development , Bristol-Myers Squibb , One Squibb Drive , New Brunswick , New Jersey 08903 , United States.
出版信息
Org Lett. 2018 Jul 6;20(13):3853-3857. doi: 10.1021/acs.orglett.8b01440. Epub 2018 Jun 11.
Abstract
A palladium(II)-catalyzed β,γ-aminohydroxylation reaction of nonconjugated alkenyl carbonyl compounds has been developed. This reaction utilizes a cleavable bidentate directing group to achieve regioselective aminopalladation. The resulting chelation-stabilized alkylpalladium(II) intermediate is then hydroxylated using oxygen/2,6-dimethylbenzoquinone in HFIP as the mild oxidation system. Under the optimized conditions, various nucleophiles and alkene substrates are capable of delivering good yields and high diastereoselectivities of the aminohydroxylated products.
摘要
钯（II）催化的非共轭烯基羰基化合物的β，γ-氨羟化反应已经被开发出来。该反应利用可裂解的双齿导向基团实现区域选择性氨钯化。所得螯合稳定的烷基钯（II）中间体然后使用 HFIP 中的氧气/2,6-二甲基苯醌作为温和的氧化体系进行羟基化。在优化条件下，各种亲核试剂和烯烃底物都能够以良好的产率和高非对映选择性得到氨羟化产物。
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