UNSPECIFIED (2001) Stiff, and sticky in the right places: The dramatic influence of preorganizing guest binding sites on the hydrogen bond-directed assembly of rotaxanes. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 123 (25). pp. 5983-5989. ISSN 0002-7863

Full text not available from this repository.

Abstract

Structural rigidity and the preorganization of thread binding sites are shown to have a major influence on template efficiency in the synthesis of hydrogen bond-assembled rotaxanes. Preorganization is so effective, in fact, that with good hydrogen bond accepters (amides) a "world record" yield of 97% for a [2]rotaxane is obtained. The truly remarkable feature of this efficient template, however, is that it allows even poor hydrogen bond accepters testers) to be used to prepare hydrogen bond-assembled rotaxanes, despite the presence of competing hydrogen bonding groups (anions) which bind the key intermediates at least 10000 x more strongly than single. unorganized, ester groups! The structures of the rotaxanes are established unambiguously in solution by H-1 NMR spectroscopy and in the solid state by X-ray crystallography. As a series they provide unique experimental information regarding the nature of amide-ester hydrogen bonding interactions; in particular they suggest that in CDCl3, amide-ester NH . . .O=C hydrogen bonds are similar to1 kcal mol(-1) weaker than the corresponding amide-amide interactions.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Publisher:	AMER CHEMICAL SOC
ISSN:	0002-7863
Date:	27 June 2001
Volume:	123
Number:	25
Number of Pages:	7
Page Range:	pp. 5983-5989
Publication Status:	Published
URI:	http://wrap.warwick.ac.uk/id/eprint/12033

Data sourced from Thomson Reuters' Web of Knowledge

Request changes to a record

Actions (login required)

View Item