Addition-substitution reactions of 2-thio-3-chloroacrylamides with carbon, nitrogen, oxygen, sulfur and selenium nucleophiles

Kissane, Marie; Murphy, Maureen; O'Brien, Elisabeth; Chopra, Jay; Murphy, Linda.; Collins, Stuart G.; Lawrence, Simon E.; Maguire, Anita R.

Addition-substitution reactions of 2-thio-3-chloroacrylamides with carbon, nitrogen, oxygen, sulfur and selenium nucleophiles

Files

MK_AdditionAV2011.pdf(1.4 MB)

Accepted Version

Date

2011-04-07

Authors

Kissane, Marie

Murphy, Maureen

O'Brien, Elisabeth

Chopra, Jay

Murphy, Linda.

Collins, Stuart G.

Lawrence, Simon E.

Maguire, Anita R.

Publisher

RSC Publishing

Published Version

10.1039/C0OB00805B

Abstract

Synthetically versatile conjugate addition of a range of carbon, nitrogen, oxygen, sulfur and selenium nucleophiles to the highly functionalised 2-thio-3-chloroacrylamides is described. The stereochemical and synthetic features of this transformation are discussed in detail. In most instances, the nucleophile replaces the chloro substituent with retention of stereochemistry. With the oxygen nucleophiles, a second addition can occur leading to acetals, while with the nitrogen nucleophiles, E-Z isomerism occurs in the resulting enamine derivatives. The ratio of the E/Z isomers can be rationalised on the basis of the substituent and the level of oxidation.

Keywords

2-thio-3-chloroacrylamides , Acetals , E-Z Isomerism , Selenium nucleophiles , Sulfur nucleophiles , Oxygen nucleophiles , Nitrogen nucleophiles , Carbon based nucleophiles

Citation

KISSANE, M., MURPHY, M., O'BRIEN, E., CHOPRA, J., MURPHY, L., COLLINS, S. G., LAWRENCE, S. E. & MAGUIRE, A. R., 2011. Addition-substitution reactions of 2-thio-3-chloroacrylamides with carbon, nitrogen, oxygen, sulfur and selenium nucleophiles. Organic & Biomolecular Chemistry, 9, 2452-2472. doi: 10.1039/C0OB00805B