Department of Chemistry, University of Pennsylvania, 231 South 34th St., Philadelphia, Pennsylvania 19104, United States.
Org Lett. 2021 Mar 5;23(5):1521-1524. doi: 10.1021/acs.orglett.0c03508. Epub 2020 Nov 11.
Organodifluorine synthons, in conjuction with three-component diastereoselective anion relay chemistry (ARC), permit ready access to diverse difluoromethylene scaffolds. Initiated via [1,2]-addition of an organolithium reagent to a β-difluoromethylene silyl aldehyde, an alkoxide intermediate is formed, which is capable of undergoing a [1,4]-Brook rearrangement to generate a stabilized α-difluoromethylene carbanion, which, upon electrophile capture, affords a three-component adduct. This three component synthetic tactic represents a novel one-pot divergent strategy for the construction of diverse organodifluorine containing compounds.
有机二氟合成子与三组分非对映选择性阴离子接力化学(ARC)相结合,可轻松获得各种二氟亚甲基支架。通过有机锂试剂对β-二氟亚甲基硅基醛的[1,2]-加成引发反应,形成烷氧基中间体,其能够经历[1,4]-Brook 重排以生成稳定的α-二氟亚甲基碳负离子,该碳负离子在亲电试剂捕获后,提供三组分加合物。这种三组分合成策略代表了一种新颖的一锅法发散策略,用于构建各种含有有机二氟的化合物。