Crystal structures and properties of mutagenic 'N'-acyloxy-'N'-alkoxyamides - 'most pyramidal' acyclic amides

Gillson, Ashley-Mae; Glover, Stephen; Tucker, David; Turner, P

doi:10.1039/b306098p

Author(s)

Gillson, Ashley-Mae

Glover, Stephen

Tucker, David

Turner, P

Publication Date

2003

Abstract

X-Ray data for two N-acyloxy-N-alkoxyamides, a class of direct-acting mutagens, indicate extreme pyramidalisationat the amide nitrogen in keeping with spectroscopic and theoretically determined properties of amides with bisoxosubstitutionat nitrogen. The combined electronegativity of two oxygens leads to average angles at nitrogen of 107.8and 108.1° and |χN| of 66° and 65°. The sp³ nature of nitrogen results in negligible amide resonance as evidencedby long N–C(O) bonds, high IR carbonyl stretch frequencies, carbonyl ¹³C NMR data and very low amideisomerisation barriers. In addition, conformations in the solid state support a strong n₀–σ*[NOAc] anomeric interactionas predicted by molecular orbital theory. HF/6-31G* calculations on formamide, N-methoxyformamide andN-formyloxy-N-methoxyformamide support these findings.

Citation

Organic & Biomolecular Chemistry, 1(0), p. 3430-3437

ISSN

1477-0539

1477-0520

Link

https://hdl.handle.net/1959.11/1347

Language

en

Publisher

Royal Society of Chemistry

Title

Crystal structures and properties of mutagenic 'N'-acyloxy-'N'-alkoxyamides - 'most pyramidal' acyclic amides

Type of document

Journal Article

Entity Type

Publication

Author(s)	Gillson, Ashley-Mae Glover, Stephen Tucker, David Turner, P
Publication Date	2003
Abstract	X-Ray data for two N-acyloxy-N-alkoxyamides, a class of direct-acting mutagens, indicate extreme pyramidalisationat the amide nitrogen in keeping with spectroscopic and theoretically determined properties of amides with bisoxosubstitutionat nitrogen. The combined electronegativity of two oxygens leads to average angles at nitrogen of 107.8and 108.1° and \|χN\| of 66° and 65°. The sp³ nature of nitrogen results in negligible amide resonance as evidencedby long N–C(O) bonds, high IR carbonyl stretch frequencies, carbonyl ¹³C NMR data and very low amideisomerisation barriers. In addition, conformations in the solid state support a strong n₀–σ[NOAc] anomeric interactionas predicted by molecular orbital theory. HF/6-31G calculations on formamide, N-methoxyformamide andN-formyloxy-N-methoxyformamide support these findings.
Citation	Organic & Biomolecular Chemistry, 1(0), p. 3430-3437
ISSN	1477-0539 1477-0520
Link	https://hdl.handle.net/1959.11/1347
Language	en
Publisher	Royal Society of Chemistry
Title	Crystal structures and properties of mutagenic 'N'-acyloxy-'N'-alkoxyamides - 'most pyramidal' acyclic amides
Type of document	Journal Article
Entity Type	Publication

Crystal structures and properties of mutagenic 'N'-acyloxy-'N'-alkoxyamides - 'most pyramidal' acyclic amides

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