The Ortho Lithiation of Tertiary Benzamides

The use of the diethyl and diisopropyl amide functions as acid oxidation level directing groups was explored. Addition of N,N-diethylbenzamide to s-BuLi-TMEDA at -78(DEGREES) in THF solution results in rapid formation of the o-lithio species. The anion was treated with D(,2)O, alkyl iodides, carbonyl compounds, ClSiMe(,3) and B(OMe)(,3) followed by H(,2)O(,2) to give the ortho substituted products in yields of 52-84%. Similarly, N-N-diisopropylbenzamide was treated with s- or n-BuLi-TMEDA followed by D(,2)O, MeOD, allyl bromide or CO(,2) to give ortho substituted products in yields of 21-87%. A mechanistic study indicated lithiation of the ortho position is direct rather than the result of rearrangement of an initially formed (alpha)-aza anion.

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

2014

Author dc:creator

• Brown, Roger Allen

• Chemistry, Organic

Language dc:language

eng

Identifier

(UMI)AAI8127554

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/67272