The endocyclic restriction test: (I) Determination of reaction pathways for the nucleophilic substitution at phosphorus by carbon. (II) Exploration of the reaction pathway of nucleophilic substitution at an oxenoid oxygen by carbon

Double labeling has been used in conjuction with the endocyclic restriction test to show that transfers of phosphorus from oxygen to carbon in the conversions of 45 to 46, of 120 to 126, of 121 to 127 and of 122 to 128 proceed in an intramolecular fashion. The transfers of a chiral phosphorus atom in the conversions of 123 to 129, of 124 to 130 and of 125 to 131 proceed with retention of stereochemistry at phosphorus. These results rule out the classic in-line S$\rm\sb N$2 pathway and the geometrically equivalent in-line addition-elimination pathway for these endocyclic transfers of phosphorus. Initial apical attack followed by pseudorotation and elimination of the apical alkoxy leaving group is suggested for these nucleophilic substitutions at phosphorus.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2011

Author dc:creator

• Tollefson, Michael Brent

Contributors dc:contributor

• Beak, Peter

• Chemistry, Organic

Statement dc:rights

• Copyright 1996 Tollefson, Michael Brent

Language dc:language

eng

Identifier

9780591199437
AAI9712461
(UMI)AAI9712461

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/20783