Journal
SCIENCE
Volume 378, Issue 6624, Pages 1085-1091Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.ade5320
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Funding
- National Institutes of Health National Institute of General Medical Sciences [R35 GM12893, R35 GM136271]
- National Science Foundation [CHE-1764328, DGE-1650604]
- US Public Health Service (USPHS) National Research Service Award [T32GM008496]
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This study reports the discovery of a highly enantioselective vinyl carbocation carbon-hydrogen (C-H) insertion reaction enabled by imidodiphosphorimidate organocatalysts. The active site confinement in this catalyst class not only allows effective enantiocontrol but also expands the scope of vinyl cation C-H insertion chemistry, enhancing the utility of this transition metal-free C(sp3)-H functionalization platform.
From the preparation of pharmaceuticals to enzymatic construction of natural products, carbocations are central to molecular synthesis. Although these reactive intermediates are engaged in stereoselective processes in nature, exerting enantiocontrol over carbocations with synthetic catalysts remains challenging. Many resonance-stabilized tricoordinated carbocations, such as iminium and oxocarbenium ions, have been applied in catalytic enantioselective reactions. However, their dicoordinated counterparts (aryl and vinyl carbocations) have not, despite their emerging utility in chemical synthesis. We report the discovery of a highly enantioselective vinyl carbocation carbon-hydrogen (C-H) insertion reaction enabled by imidodiphosphorimidate organocatalysts. Active site confinement featured in this catalyst class not only enables effective enantiocontrol but also expands the scope of vinyl cation C-H insertion chemistry, which broadens the utility of this transition metal-free C(sp3)-H functionalization platform.
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