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. 2022 May 6;2(5):1071-1077.
doi: 10.1021/jacsau.2c00186. eCollection 2022 May 23.

Cobalt-Catalyzed Cyclization of Unsaturated N-Acyl Sulfonamides: a Diverted Mukaiyama Hydration Reaction

David M Fischer  1 , Moritz Balkenhohl  1 , Erick M Carreira  1
Affiliations

Cobalt-Catalyzed Cyclization of Unsaturated N-Acyl Sulfonamides: a Diverted Mukaiyama Hydration Reaction

David M Fischer et al. JACS Au. .

Abstract

The cycloisomerization of β-, γ-, and δ-unsaturated N-acyl sulfonamides to N-sulfonyl lactams and imidates is reported. This transformation is effected in the presence of a CoIII(salen) catalyst using t-BuOOH or air as the oxidant. The method shows good functional group tolerance (alkyl, aryl, heteroaryl, ether, N-Boc) and furnishes an underexplored class of cyclic building blocks. The strong solvent dependence of the transformation is investigated, and the synthetic versatility of the N-sulfonyl imidate product class is highlighted.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Cyclization of Alkenyl N-Acyl Sulfonamides
Figure 1
Figure 1
Background and initial observations.
Figure 2
Figure 2
Substrate scope of the Co-catalyzed cycloisomerization of alkenyl N-acyl sulfonamides. aReaction yield obtained employing 10 mol%1, 4 equiv of PhSiH3, and air. bThermal ellipsoids are shown at the 50% probability level.
Figure 3
Figure 3
Co-catalyzed cycloisomerization of a variety of sulfonamide and sulfinamide derivatives.
Figure 4
Figure 4
Control experiments for the Co-catalyzed cycloisomerization reaction.
Figure 5
Figure 5
Determination of the barrier to E/Z isomerization in N-sulfonyl imidate 4a. 1H NMR spectra were recorded at 500 MHz in toluene-d8 at −60 to 100 °C.
Figure 6
Figure 6
Selected functionalization of sulfonyl imidates.
Figure 7
Figure 7
Solvent trends in the cycloisomerization of N-acyl sulfonamides. (A) Product distribution in various solvents. (B) Relationship between solvent donor number (Gutmann) and yield of 4a. (C) Correlation between S (=4a/(4a + I + II)) and solvent donor number.
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