Stereochemical Studies of Thermal Intermolecular and Intramolecular N-Sulfonylimine Ene Reactions

David M. Tschaen, Edward Turos, Steven M. Weinreb

Research output: Contribution to journalArticle

96 Citations (Scopus)

Abstract

N-Sulfonylimine 2 has been found to undergo highly stereoselective thermal ene reactions with cyclohexene and trans-2-butene. In the cyclohexene example, the exclusive product was unsaturated amino acid derivative 6, the product of an endo transition state. With trans-2-butene, a 9:1 mixture of 18:22 was obtained, with the endo product again predominating. Intramolecular ene processes have been effected with the N-sulfonylimines derived from glyoxylates 25c and 26c. In the former case, the sole ene product was γ-lactone 30 derived from exo addition. In the latter process, a 9:1 mixture of cis-(E)-lactone 32 and cw-(Z)-lactone 33 was produced. Lactone 32 results from endo ene transition state 35 and 33 results from endo transition state 36. All attempts to effect intermolecular ene reactions of N-benzoylimine 39 failed. In trying to perform an intramolecular N-acylimine ene reaction, only Diels-Alder adduct 45 was produced from precursor 42.

Original languageEnglish (US)
Pages (from-to)5058-5064
Number of pages7
JournalJournal of Organic Chemistry
Volume49
Issue number26
DOIs
StatePublished - Dec 1984

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Lactones
Glyoxylates
Derivatives
Amino Acids
Hot Temperature
N-sulfonylimine
2-butene
cyclohexene

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

Cite this

Tschaen, David M. ; Turos, Edward ; Weinreb, Steven M. / Stereochemical Studies of Thermal Intermolecular and Intramolecular N-Sulfonylimine Ene Reactions. In: Journal of Organic Chemistry. 1984 ; Vol. 49, No. 26. pp. 5058-5064.
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Stereochemical Studies of Thermal Intermolecular and Intramolecular N-Sulfonylimine Ene Reactions. / Tschaen, David M.; Turos, Edward; Weinreb, Steven M.

In: Journal of Organic Chemistry, Vol. 49, No. 26, 12.1984, p. 5058-5064.

Research output: Contribution to journalArticle

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N2 - N-Sulfonylimine 2 has been found to undergo highly stereoselective thermal ene reactions with cyclohexene and trans-2-butene. In the cyclohexene example, the exclusive product was unsaturated amino acid derivative 6, the product of an endo transition state. With trans-2-butene, a 9:1 mixture of 18:22 was obtained, with the endo product again predominating. Intramolecular ene processes have been effected with the N-sulfonylimines derived from glyoxylates 25c and 26c. In the former case, the sole ene product was γ-lactone 30 derived from exo addition. In the latter process, a 9:1 mixture of cis-(E)-lactone 32 and cw-(Z)-lactone 33 was produced. Lactone 32 results from endo ene transition state 35 and 33 results from endo transition state 36. All attempts to effect intermolecular ene reactions of N-benzoylimine 39 failed. In trying to perform an intramolecular N-acylimine ene reaction, only Diels-Alder adduct 45 was produced from precursor 42.

AB - N-Sulfonylimine 2 has been found to undergo highly stereoselective thermal ene reactions with cyclohexene and trans-2-butene. In the cyclohexene example, the exclusive product was unsaturated amino acid derivative 6, the product of an endo transition state. With trans-2-butene, a 9:1 mixture of 18:22 was obtained, with the endo product again predominating. Intramolecular ene processes have been effected with the N-sulfonylimines derived from glyoxylates 25c and 26c. In the former case, the sole ene product was γ-lactone 30 derived from exo addition. In the latter process, a 9:1 mixture of cis-(E)-lactone 32 and cw-(Z)-lactone 33 was produced. Lactone 32 results from endo ene transition state 35 and 33 results from endo transition state 36. All attempts to effect intermolecular ene reactions of N-benzoylimine 39 failed. In trying to perform an intramolecular N-acylimine ene reaction, only Diels-Alder adduct 45 was produced from precursor 42.

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