化学
区域选择性
卡宾
激进的
双生的
组合化学
催化作用
氨基酸
光催化
脱质子化
猝灭(荧光)
光催化
分子
有机化学
立体化学
荧光
离子
生物化学
物理
量子力学
作者
Nao Tanaka,Joshua Zhu,Oniya L. Valencia,Cullen R. Schull,Karl A. Scheidt
摘要
β-Amino acids are useful building blocks of bioactive molecules, including peptidomimetics and pharmaceutical compounds. The current limited accessibility to β2,2-type amino acids which bear an α-quaternary center has limited their use in chemical synthesis and biological investigations. Disclosed herein is the development of a new N-heterocyclic carbene/photocatalyzed aminocarboxylation of olefins, affording β2,2-amino esters with high regioselectivity. The generation of nitrogen-centered radicals derived from simple imides via a sequence of deprotonation and single-electron oxidation allows for the subsequent addition to geminal-disubstituted olefins regioselectively. The intermediate tertiary radicals then cross-couple with a stabilized azolium-based radical generated in situ to efficiently construct the quaternary centers. Mechanistic studies, including Stern–Volmer fluorescence quenching experiments, support the proposed catalytic cycle.
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