英国剑桥大学Robert J. Phipps研究小组在研究中取得进展。他们研究了酰胺的氢原子转移驱动的对映选择性Minisci反应。 该项研究成果发表在2021年3月29日出版的《美国化学会杂志》上。

研究团队公开了一种方法，使线性酰胺和杂芳烃的这种偶联能够完全控制新形成的对映选择性以及杂芳烃和酰胺的位点选择性。这是通过使用手性磷酸催化剂与双乙酰结合作为氢原子转移试剂和氧化剂实现的。双乙酰是直接光激发的，因此，不需要外源光催化剂——一个有助于该方法简单性和实用性的额外功能。

据了解，Minisci反应是在基本异质芳烃周围建立复杂性的最有力的方法之一。最理想的变体涉及每个配偶体上C–H键的正式氧化偶联，从而导致最简单的起始原料。

附：英文原文

Title: Hydrogen Atom Transfer-Driven Enantioselective Minisci Reaction of Amides

Author: Rupert S. J. Proctor, Padon Chuentragool, Avene C. Colgan, Robert J. Phipps

Issue&Volume: March 29, 2021

Abstract: Minisci-type reactions constitute one of the most powerful methods for building up complexity around basic heteroarenes. The most desirable variants involve formal oxidative coupling of a C–H bond on each partner, leading back to the simplest possible starting materials. We herein disclose a method that enables such a coupling of linear amides and heteroarenes with full control of enantioselectivity at the newly formed stereocenter as well as site selectivity on both the heteroarene and the amide. This is achieved by the use of a chiral phosphoric acid catalyst in conjunction with diacetyl as a combined hydrogen atom transfer reagent and oxidant. Diacetyl is directly photoexcitable, and thus, no extraneous photocatalyst is required: an added feature that contributes to the simplicity and practicality of the protocol.

DOI: 10.1021/jacs.1c01556

Source: https://pubs.acs.org/doi/10.1021/jacs.1c01556