| Autor: |
Sakai HA; Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States., MacMillan DWC; Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States. |
| Jazyk: |
angličtina |
| Zdroj: |
Journal of the American Chemical Society [J Am Chem Soc] 2022 Apr 13; Vol. 144 (14), pp. 6185-6192. Date of Electronic Publication: 2022 Mar 30. |
| DOI: |
10.1021/jacs.2c02062 |
| Abstrakt: |
Alcohols and carboxylic acids are among the most commercially abundant, synthetically versatile, and operationally convenient functional groups in organic chemistry. Under visible light photoredox catalysis, these native synthetic handles readily undergo radical activation, and the resulting open-shell intermediates can subsequently participate in transition metal catalysis. In this report, we describe the C( sp 3 )-C( sp 3 ) cross-coupling of alcohols and carboxylic acids through the dual combination of N -heterocyclic carbene (NHC)-mediated deoxygenation and hypervalent iodine-mediated decarboxylation. This mild and practical Ni-catalyzed radical-coupling protocol was employed to prepare a wide array of alkyl-alkyl cross-coupled products, including highly congested quaternary carbon centers from the corresponding tertiary alcohols or tertiary carboxylic acids. We demonstrate the synthetic applications of this methodology to alcohol C 1 -alkylation and formal homologation, as well as to the late-stage functionalization of drugs, natural products, and biomolecules. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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