Carbon quaternization of redox active esters and olefins by decarboxylative coupling.

Autor: Gan XC; Department of Chemistry, Scripps Research, La Jolla, CA 92037, USA., Zhang B; Department of Chemistry, Scripps Research, La Jolla, CA 92037, USA., Dao N; Department of Chemistry, Scripps Research, La Jolla, CA 92037, USA., Bi C; Department of Chemistry, Scripps Research, La Jolla, CA 92037, USA., Pokle M; Department of Chemistry, Scripps Research, La Jolla, CA 92037, USA., Kan L; Department of Chemistry, Scripps Research, La Jolla, CA 92037, USA.; College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China., Collins MR; Oncology Medicinal Chemistry Department, Pfizer Pharmaceuticals, San Diego, CA 92122, USA., Tyrol CC; Pfizer Medicine Design, Groton, CT 06340, USA., Bolduc PN; Biogen Inc., Cambridge, MA 02142, USA., Nicastri M; Biogen Inc., Cambridge, MA 02142, USA., Kawamata Y; Department of Chemistry, Scripps Research, La Jolla, CA 92037, USA., Baran PS; Department of Chemistry, Scripps Research, La Jolla, CA 92037, USA., Shenvi R; Department of Chemistry, Scripps Research, La Jolla, CA 92037, USA.
Jazyk: angličtina
Zdroj: Science (New York, N.Y.) [Science] 2024 Apr 05; Vol. 384 (6691), pp. 113-118. Date of Electronic Publication: 2024 Apr 04.
DOI: 10.1126/science.adn5619
Abstrakt: The synthesis of quaternary carbons often requires numerous steps and complex conditions or harsh reagents that act on heavily engineered substrates. This is largely a consequence of conventional polar-bond retrosynthetic disconnections that in turn require multiple functional group interconversions, redox manipulations, and protecting group chemistry. Here, we report a simple catalyst and reductant combination that converts two types of feedstock chemicals, carboxylic acids and olefins, into tetrasubstituted carbons through quaternization of radical intermediates. An iron porphyrin catalyst activates each substrate by electron transfer or hydrogen atom transfer, and then combines the fragments using a bimolecular homolytic substitution (S H 2) reaction. This cross-coupling reduces the synthetic burden to procure numerous quaternary carbon---containing products from simple chemical feedstocks.
Databáze: MEDLINE
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