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. 2017 Mar 1;8(3):2431-2435.
doi: 10.1039/c6sc05026c. Epub 2016 Dec 20.

Cobalt catalyzed carbonylation of unactivated C(sp3)-H bonds

Nagaraju Barsu  1 , Shyam Kumar Bolli  1 , Basker Sundararaju  1
Affiliations

Cobalt catalyzed carbonylation of unactivated C(sp3)-H bonds

Nagaraju Barsu et al. Chem Sci. .

Abstract

A general efficient regioselective cobalt catalyzed carbonylation of unactivated C(sp3)-H bonds of aliphatic amides was demonstrated using atmospheric (1-2 atm) carbon monoxide as a C1 source. This straightforward approach provides access to α-spiral succinimide regioselectively in a good yield. Cobalt catalyzed sp3 C-H bond carbonylation is reported for the first time including the functionalization of (β)-C-H bonds of α-1°, 2°, 3° carbons and even internal (β)-C-H bonds. Our initial mechanistic investigation reveals that the C-H activation step is irreversible and will possibly be the rate determining step.

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Figures

Scheme 1
Scheme 1. Carbonylation of unactivated C(sp3)–H bonds.
Scheme 2
Scheme 2. Gram scale synthesis of succinimide.
Scheme 3
Scheme 3. Scope and limitation. aThe number in parenthesis is the ratio of diastereomer. b36 h instead of 24 h. cPhCl as a solvent.
Scheme 4
Scheme 4. H/D exchange, KIE and control experiments.
Scheme 5
Scheme 5. Proposed mechanism.
Scheme 6
Scheme 6. Synthetic applications.
See this image and copyright information in PMC

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