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Combs JR, Lai YC, Van Vranken DL. Tandem Insertion/[3,3]-Sigmatropic Rearrangement Involving the Formation of Silyl Ketene Acetals by Insertion of Rhodium Carbenes into S-Si Bonds. Org Lett. 2021;23(8):2841-2845doi: 10.1021/acs.orglett.1c00229.
Combs, J. R., Lai, Y. C., & Van Vranken, D. L. (2021). Tandem Insertion/[3,3]-Sigmatropic Rearrangement Involving the Formation of Silyl Ketene Acetals by Insertion of Rhodium Carbenes into S-Si Bonds. Organic letters, 23(8), 2841-2845. https://doi.org/10.1021/acs.orglett.1c00229
Combs, Jason R, et al. "Tandem Insertion/[3,3]-Sigmatropic Rearrangement Involving the Formation of Silyl Ketene Acetals by Insertion of Rhodium Carbenes into S-Si Bonds." Organic letters vol. 23,8 (2021): 2841-2845. doi: https://doi.org/10.1021/acs.orglett.1c00229
Combs JR, Lai YC, Van Vranken DL. Tandem Insertion/[3,3]-Sigmatropic Rearrangement Involving the Formation of Silyl Ketene Acetals by Insertion of Rhodium Carbenes into S-Si Bonds. Org Lett. 2021 Apr 16;23(8):2841-2845. doi: 10.1021/acs.orglett.1c00229. Epub 2021 Apr 01. PMID: 33792331.
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Org Lett. 2021 Apr 16;23(8):2841-2845. doi: 10.1021/acs.orglett.1c00229. Epub 2021 Apr 01.

Tandem Insertion/[3,3]-Sigmatropic Rearrangement Involving the Formation of Silyl Ketene Acetals by Insertion of Rhodium Carbenes into S-Si Bonds.

Organic letters

Jason R Combs, Yin-Chu Lai, David L Van Vranken

Affiliations

  1. Department of Chemistry, University of California, Irvine, Irvine, California 92617, United States.

PMID: 33792331 DOI: 10.1021/acs.orglett.1c00229

Abstract

Allyl 2-diazo-2-phenylacetates are shown to react with trimethylsilyl thioethers in the presence of rhodium(II) catalysts to generate α-allyl-α-thio silyl esters. The transformation involves a tandem process involving formal rhodium-catalyzed insertion of the carbene group into the S-Si bond to generate a silyl ketene acetal, followed by a spontaneous Ireland-Claisen rearrangement. The silyl ester products were isolated as the corresponding carboxylic acids after aqueous workup. Intramolecular cyclopropanation of the allyl fragment generally competes with addition of the heteroatom to the carbene center. The reaction occurs under mild conditions and in high yield, allowing for rapid entry into rearrangement tetrasubstituted products. Propargyl esters were shown to generate the corresponding α-allenyl products.

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