Carbon-carbon bond-forming reactions of α-thioaryl carbonyl compounds for the synthesis of complex heterocyclic molecules

James E. Biggs-Houck, Rebecca L. Davis, Jingqiang Wei, Brandon Q. Mercado, Marilyn M. Olmstead, Dean J. Tantillo, Jared T. Shaw

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Strategies for the formation of carbon-carbon bonds from the α-thioaryl carbonyl products of substituted lactams are described. Although direct functionalization is possible, a two step process of oxidation and magnesium-sulfoxide exchange has proven optimal. The oxidation step results in the formation of two diastereomers that exhibit markedly different levels of stability toward elimination, which is rationalized on the basis of quantum mechanical calculations and X-ray crystallography. Treatment of the sulfoxide with i-PrMgCl results in the formation of a magnesium enolate that will undergo an intramolecular Michael addition reaction to form two new stereogenic centers. The relationship between the substitution patterns of the sulfoxide substrate and the efficiency of the magnesium exchange reaction are also described.

Original languageEnglish (US)
Pages (from-to)160-172
Number of pages13
JournalJournal of Organic Chemistry
Volume77
Issue number1
DOIs
StatePublished - Jan 6 2012

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sulfoxide
Carbonyl compounds
Magnesium
Carbon
Molecules
Lactams
Oxidation
Addition reactions
X ray crystallography
Ion exchange
Substitution reactions
Substrates

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Biggs-Houck, J. E., Davis, R. L., Wei, J., Mercado, B. Q., Olmstead, M. M., Tantillo, D. J., & Shaw, J. T. (2012). Carbon-carbon bond-forming reactions of α-thioaryl carbonyl compounds for the synthesis of complex heterocyclic molecules. Journal of Organic Chemistry, 77(1), 160-172. https://doi.org/10.1021/jo201541e

Carbon-carbon bond-forming reactions of α-thioaryl carbonyl compounds for the synthesis of complex heterocyclic molecules. / Biggs-Houck, James E.; Davis, Rebecca L.; Wei, Jingqiang; Mercado, Brandon Q.; Olmstead, Marilyn M.; Tantillo, Dean J.; Shaw, Jared T.

In: Journal of Organic Chemistry, Vol. 77, No. 1, 06.01.2012, p. 160-172.

Research output: Contribution to journalArticle

Biggs-Houck, JE, Davis, RL, Wei, J, Mercado, BQ, Olmstead, MM, Tantillo, DJ & Shaw, JT 2012, 'Carbon-carbon bond-forming reactions of α-thioaryl carbonyl compounds for the synthesis of complex heterocyclic molecules', Journal of Organic Chemistry, vol. 77, no. 1, pp. 160-172. https://doi.org/10.1021/jo201541e
Biggs-Houck, James E. ; Davis, Rebecca L. ; Wei, Jingqiang ; Mercado, Brandon Q. ; Olmstead, Marilyn M. ; Tantillo, Dean J. ; Shaw, Jared T. / Carbon-carbon bond-forming reactions of α-thioaryl carbonyl compounds for the synthesis of complex heterocyclic molecules. In: Journal of Organic Chemistry. 2012 ; Vol. 77, No. 1. pp. 160-172.
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