Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Chemistry Department, Faculty of Science, King Abdulaziz University (KAU), 21589, Jeddah, Saudi Arabia.
Angew Chem Int Ed Engl. 2016 Aug 1;55(32):9416-21. doi: 10.1002/anie.201602347. Epub 2016 Jun 28.
An unprecedented and challenging radical-radical cross-coupling of α-aminoalkyl radicals with monofluoroalkenyl radicals derived from gem-difluoroalkenes was achieved. This first example of tandem C(sp(3) )-H and C(sp(2) )-F bond functionalization through visible-light photoredox catalysis offers a facile and flexible access to privileged tetrasubstituted monofluoroalkenes under very mild reaction conditions. The striking features of this redox-neutral method in terms of scope, functional-group tolerance, and regioselectivity are illustrated by the late-stage fluoroalkenylation of complex molecular architectures such as bioactive (+)-diltiazem, rosiglitazone, dihydroartemisinin, oleanic acid, and androsterone derivatives, which represent important new α-amino C-H monofluoroalkenylations.
实现了前所未有的、具有挑战性的α-氨烷基自由基与源自偕二氟烯烃的单氟烯基自由基的自由基-自由基交叉偶联。首例通过可见光光氧化还原催化实现的串联 C(sp(3) )-H 和 C(sp(2) )-F 键官能化的实例，为在非常温和的反应条件下获得手性四取代单氟烯烃提供了一种简便、灵活的方法。该还原-中性方法在范围、官能团耐受性和区域选择性方面的显著特点，通过生物活性(+)-地尔硫卓、罗格列酮、二氢青蒿素、齐墩果酸和雄甾酮衍生物等复杂分子结构的晚期氟烯基化反应得到了说明，这些反应代表了重要的新的α-氨基 C-H 单氟烯基化反应。
