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. 2024 Dec 20;26(50):10708-10713.
doi: 10.1021/acs.orglett.4c03558. Epub 2024 Dec 11.

A Catalytic, Enantioselective Sulfamate Tethered Aza-Michael Cyclization

Harshit Joshi  1 , Abhijit Manna  1 , Someshwar Nagamalla  1 , Annu Anna Thomas  1 , Shyam Sathyamoorthi  1
Affiliations

A Catalytic, Enantioselective Sulfamate Tethered Aza-Michael Cyclization

Harshit Joshi et al. Org Lett. .

Abstract

We show the first examples of enantioselective cyclization reactions of tethered sulfamates onto pendant α,β-unsaturated esters, ketones, and thioesters. This reaction is promoted by a new chiral bifunctional guanidine catalyst and is operationally very simple. A variety of primary sulfamates and sulfamides were examined, and in many cases, products were delivered in excellent yields and enantiomeric ratios. With secondary sulfamates, kinetic resolutions were possible. The product oxathiazinanes are very useful chiral synthons.

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Figures

Scheme 1.
Scheme 1.
Enantioselective aza-michael reactions with α,β-unsaturated esters is challenging.
Scheme 2.
Scheme 2.
Effect of N-substituents on yield and enantioselectivity.
Scheme 3.
Scheme 3.
Substrate scope exploration.
Scheme 4.
Scheme 4.
Kinetic resolutions are possible with secondary sulfamates.
Scheme 5.
Scheme 5.
Scale up and product diversification.
See this image and copyright information in PMC

References

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