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. 2023 Jul 25;3(5):291-298.
doi: 10.1021/acsorginorgau.3c00024. eCollection 2023 Oct 4.

Pd-Catalyzed Regioselective Cyclopropanation of 2-Substituted 1,3-Dienes

Agonist Kastrati  1 , Vincent Jaquier  1 , Michele Garbo  1 , Céline Besnard  2 , Clément Mazet  1
Affiliations

Pd-Catalyzed Regioselective Cyclopropanation of 2-Substituted 1,3-Dienes

Agonist Kastrati et al. ACS Org Inorg Au. .

Abstract

A Pd-catalyzed 3,4-regioselective cyclopropanation of 2-substituted 1,3-dienes by decomposition of diazo esters is reported. The vinylcyclopropanes generated are isolated in practical chemical yields with high levels of regioselectivity but low diastereoselectivity. The system operates under mild reaction conditions, is scalable, and tolerates various sensitive functional groups. A series of original postcatalytic derivatizations is presented to highlight the synthetic potential of the catalytic method.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
(A) Cu-catalyzed enantioselective cyclopropanation of DMHD. (B) Cu-catalyzed 1,2-regioselective and enantioselective cyclopropanation of branched dienes. (C) Ni-catalyzed 1,2-regioselective, and diastereoselective cyclopropanation of 2-substituted 1,3-dienes. (D) Pd-catalyzed 3,4-regioselective cyclopropanation of 2-substituted 1,3-dienes.
Figure 2
Figure 2
Scope of the Pd-catalyzed 3,4-regioselective cyclopropanation of 2-substituted 1,3-dienes (0.5 mmol scale). Regio- and diastereoselectivity determined by 1H NMR. Yield after purification.
Figure 3
Figure 3
Pd-catalyzed cyclopropanation of differently substituted 1,3-dienes (0.5–1.0 mmol scale). Regio- and diastereoselectivity determined by 1H NMR. aNot determined.
Figure 4
Figure 4
Large-scale experiment. Regio- and diastereoselectivity determined by 1H NMR.
Figure 5
Figure 5
(A) Simmons–Smith–Furukawa cyclopropanations, (B) V-catalyzed epoxidations, and (C) Cu-catalyzed borylative ring-opening reactions.
See this image and copyright information in PMC

References

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