Stereogenic propargylic centers via base-mediated terminal allne isomerization

John D. Spence, Justin K. Wyatt, Daniel M. Bender, David K. Moss, Michael H. Nantz

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

A study of alkali metal amide-mediated isomerizations of terminal allenes is described. The isomerizations of substituted ethenylidenecyclohexanes to form diastereomeric mixtures of terminal alkynes have been conducted to determine factors which may influence the stereochemistry at the newly formed propargylic centers. An initial base screen revealed that potassium N-methylbutylamide (KMBA) exhibits the highest level of equatorial to axial alkyne diastereoselectivity. With the severely hindered terminal allene 26, the use of potassium 3-aminopropylamide is required to effect isomerization. A general synthesis of deuterated terminal allenes has also been achieved, and a mechanistic study using d2-allenes 18a,b has revealed the involvement of a propargylic anion in the course of the KMBA-mediated isomerizations.

Original languageEnglish (US)
Pages (from-to)4014-4021
Number of pages8
JournalJournal of Organic Chemistry
Volume61
Issue number12
StatePublished - Jun 14 1996

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Isomerization
Alkynes
Potassium
Alkali Metals
Stereochemistry
Amides
Anions
propadiene
2-keto-4-mercaptobutyric acid

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Spence, J. D., Wyatt, J. K., Bender, D. M., Moss, D. K., & Nantz, M. H. (1996). Stereogenic propargylic centers via base-mediated terminal allne isomerization. Journal of Organic Chemistry, 61(12), 4014-4021.

Stereogenic propargylic centers via base-mediated terminal allne isomerization. / Spence, John D.; Wyatt, Justin K.; Bender, Daniel M.; Moss, David K.; Nantz, Michael H.

In: Journal of Organic Chemistry, Vol. 61, No. 12, 14.06.1996, p. 4014-4021.

Research output: Contribution to journalArticle

Spence, JD, Wyatt, JK, Bender, DM, Moss, DK & Nantz, MH 1996, 'Stereogenic propargylic centers via base-mediated terminal allne isomerization', Journal of Organic Chemistry, vol. 61, no. 12, pp. 4014-4021.
Spence JD, Wyatt JK, Bender DM, Moss DK, Nantz MH. Stereogenic propargylic centers via base-mediated terminal allne isomerization. Journal of Organic Chemistry. 1996 Jun 14;61(12):4014-4021.
Spence, John D. ; Wyatt, Justin K. ; Bender, Daniel M. ; Moss, David K. ; Nantz, Michael H. / Stereogenic propargylic centers via base-mediated terminal allne isomerization. In: Journal of Organic Chemistry. 1996 ; Vol. 61, No. 12. pp. 4014-4021.
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