Department of Chemistry, University of California, Irvine, Irvine, CA, 92697, USA.
Discovery Chemistry, Merck & Co., Inc., Boston, MA, 02115, USA.
Angew Chem Int Ed Engl. 2021 Sep 1;60(36):19660-19664. doi: 10.1002/anie.202105679. Epub 2021 Aug 1.
We report the first enantioselective addition of pyrazoles to 1,3-dienes. Secondary and tertiary allylic pyrazoles can be generated with excellent regioselectivity. Mechanistic studies support a pathway distinct from previous hydroaminations: a Pd -catalyzed ligand-to-ligand hydrogen transfer (LLHT). This hydroamination tolerates a range of functional groups and advances the field of diene hydrofunctionalization.
我们报告了首例吡唑对 1,3-二烯的对映选择性加成。仲和叔烯丙基吡唑可以极好的区域选择性生成。机理研究支持一条与先前的氢胺化不同的途径:Pd 催化的配体到配体的氢转移(LLHT)。这种氢胺化能够容忍一系列官能团,并推动了二烯氢官能化领域的发展。