Stereoselective hydrogen atom transfer to acyclic radicals: a switch enabling diastereodivergent borylative radical cascades

Tian Ye, Feng-Lian Zhang, Hui-Min Xia, Xi Zhou, Zhi-Xiang Yu () and Yi-Feng Wang ()
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Tian Ye: University of Science and Technology of China
Feng-Lian Zhang: University of Science and Technology of China
Hui-Min Xia: University of Science and Technology of China
Xi Zhou: University of Science and Technology of China
Zhi-Xiang Yu: Peking University
Yi-Feng Wang: University of Science and Technology of China

Nature Communications, 2022, vol. 13, issue 1, 1-12

Abstract: Abstract Radical cascade reactions are powerful tools to construct structurally complex molecules. However, the stereochemical control of acyclic radical intermediates remains a persistent challenge, due to the low differentiation between the two faces of these species. This hurdle further makes stereodivergent synthesis rather more difficult to be accomplished, in particular for intermediates resulted from complex cascades. Here we report an efficient strategy for stereoselective hydrogen atom transfer (HAT) to acyclic carbon radicals, which are generated via N-heterocyclic carbene (NHC)-boryl radicals triggered addition-translocation-cyclization cascades. A synergistic control by the NHC subunit and a thiol catalyst has proved effective for one facial HAT, while a ZnI2-chelation protocol allows for the preferential reaction to the opposite face. Such a stereoselectivity switch enables diastereodivergent construction of heterocycles tethering a boron-substituted stereocenter. Mechanistic studies suggest two complementary ways to tune HAT diastereoselectivity. The stereospecific conversions of the resulting boron-handled products to diverse functionalized molecules are demonstrated.

Date: 2022
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DOI: 10.1038/s41467-022-28071-8

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