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. 2022 Nov 4;87(21):13517-13528.
doi: 10.1021/acs.joc.2c00978. Epub 2022 Oct 20.

Asymmetric Cyclopropanation with 4-Aryloxy-1-sulfonyl-1,2,3-triazoles: Expanding the Range of Rhodium-Stabilized Donor/Acceptor Carbenes to Systems with an Oxygen Donor Group

Robert W Kubiak 2nd  1 , William F Tracy  1 , Joshua S Alford  1 , Huw M L Davies  1
Affiliations

Asymmetric Cyclopropanation with 4-Aryloxy-1-sulfonyl-1,2,3-triazoles: Expanding the Range of Rhodium-Stabilized Donor/Acceptor Carbenes to Systems with an Oxygen Donor Group

Robert W Kubiak 2nd et al. J Org Chem. .

Abstract

Rhodium-catalyzed enantioselective synthesis of 1-phenoxycyclopropane-1-carbaldehydes by intermolecular cyclopropanation of terminal alkenes followed by imine hydrolysis is described. This methodology utilizes 4-aryloxy-1-sulfonyl-1,2,3-triazoles as the carbene precursors and the chiral dirhodium(II) tetracarboxylates Rh2(S-NTTL)4 or Rh2(S-DPCP)4 as the catalysts. These reactions are considered to proceed via rhodium-stabilized donor/acceptor carbene intermediates, and these studies demonstrate that a heteroatom donor group is compatible with an enantioselective transformation.

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Conflict of interest statement

HMLD is a named inventor on a patent entitled, Dirhodium Catalyst Compositions and Synthetic Processes Related Thereto (US 8,974,428, issued March 10, 2015). The other authors have no competing financial interests.

Figures

Figure 1.
Figure 1.
React IR comparison of a thermal reaction versus a rhodium catalyzed reaction of 1.
Figure 2.
Figure 2.
X-ray crystal structure of 4a.
Scheme 1.
Scheme 1.
Classes of metal-stabilized carbenes
Scheme 2.
Scheme 2.
Most widely used precursors to donor/acceptor carbenes
Scheme 3.
Scheme 3.
Catalyst influence on reaction outcome
See this image and copyright information in PMC

References

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