Anchimeric-Assisted Spontaneous Hydrolysis of Cyanohydrins Under Ambient Conditions: Implications for Cyanide-Initiated Selective Transformations

Jayasudhan Reddy Yerabolu; Charles L Liotta; Ramanarayanan Krishnamurthy

doi:10.1002/chem.201701497

Anchimeric-Assisted Spontaneous Hydrolysis of Cyanohydrins Under Ambient Conditions: Implications for Cyanide-Initiated Selective Transformations

Chemistry. 2017 Jun 27;23(36):8756-8765. doi: 10.1002/chem.201701497. Epub 2017 Jun 13.

Authors

Jayasudhan Reddy Yerabolu^{1

2}, Charles L Liotta^{3

2}, Ramanarayanan Krishnamurthy^{1

2}

Affiliations

¹ Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Rd, La Jolla, CA, 92037, USA.
² NSF-NASA Center for Chemical Evolution, Atlanta, GA, 30332, USA.
³ School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, GA, 30332, USA.

PMID: 28474360
DOI: 10.1002/chem.201701497

Abstract

Nitrile/cyanide hydrolysis is of importance from the perspective of organic chemistry, especially, prebiotic chemistry. Herein we report that cyanohydrins, generated by the reaction of cyanide with β-keto acids and γ-keto-alcohols, spontaneously hydrolyze under ambient conditions (aqueous medium, RT, and a range of pH). The spontaneous hydrolysis is affected by an intramolecular proton transfer and an intramolecular 5-exo-dig attack, but with a twist. In the case of β-keto acids, the hydrolysis is mediated by the neighboring carboxylic acid group only at pH values less than 7, whereas in the case of γ-keto-alcohols the hydrolysis is mediated by the neighboring hydroxyl group only at pH values greater than 7. The results, in combination with previous works, have implications for selective transformations of cyanide-initiated prebiotic systems chemistry.

Keywords: anchimeric assistance; cyanides; hydrolysis; prebiotic systems chemistry; α-hydroxy amides.