Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 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.

PubMed Disclaimer

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

Similar articles

See all similar articles

Cited by

References

    1. For an overview of reactions of rhodium metallocarbenes, and a more detailed overview of different classes of rhodium catalysts and diazo compounds, see:
    2. Davies HML Finding Opportunities from Surprises and Failures. Development of Rhodium-Stabilized Donor/Acceptor Carbenes and Their Application to Catalyst-Controlled C−H Functionalization. J. Org. Chem 2019, 84, 12722–12745, and references cited therein. - PMC - PubMed
    1. For a recent review of the utility of diazo compounds as carbene precursors in organic synthesis, see:
    2. Dong S; Liu X; Feng X Asymmetric Catalytic Rearrangements with α-Diazocarbonyl Compounds. Acc. Chem. Res 2022, 55, 415–428. - PubMed
    1. For a general overview of reactions of N-sulfonyl-1,2,3-triazoles, see:
    2. Davies HML; Alford JS Reactions of Metallocarbenes Derived from Nsulfonyl-1,2,3-triazoles. Chem. Soc. Rev, 2014, 43, 5151–5162. - PubMed
    1. Alford JS; Davies HML Expanding the Scope of Donor/Acceptor Carbenes to N-Phthalimido Donor Groups: Diastereoselective Synthesis of 1-Cyclopropane α-Amino Acids. Org. Lett 2012, 14, 6020–6023. - PubMed
    2. Wilkerson-Hill SM; Haines BE; Musaev DG; Davies HML Synthesis of [3a,7a]-Dihydroindoles by a Tandem Arene Cyclopropanation/3,5-Sigmatropic Rearrangement Reaction. J. Org. Chem 2018, 83, 7939–7949. - PMC - PubMed
    1. For initial work demonstrating the formation of latent diazos from N-sulfonyltriazoles, see:
    2. Chuprakov S; Kwok SW; Zhang L; Lercher L; Fokin VV Rhodium-Catalyzed Enantioselective Cyclopropanation of Olefins with N-Sulfonyl 1,2,3-Triazoles. J. Am. Chem. Soc 2009, 131, 18034–18035. - PMC - PubMed
    3. Grimster N; Zhang L; Fokin VV Synthesis and Reactivity of Rhodium(II) N-Triflyl Azavinyl Carbenes. J. Am. Chem. Soc 2010, 132, 2510–2511. - PMC - PubMed

Publication types