Asymmetric Nitroalkene [4 + 2] Cycloadditions: Enantioselective Synthesis of 3-Substituted and 3,4-Disubstituted Pyrrolidines

Scott E. Denmark, Lawrence R. Marcin

Research output: Contribution to journalArticle

Abstract

2-Substituted 1-nitroalkenes undergo highly diastereoselective, Lewis-acid-promoted, [4 + 2] cycloaddition with chiral vinyl ethers derived from (R)-2,2-diphenylcyclopentanol and (1R,2S)-2-phenylcyclohexanol to afford cyclic nitronates in high yields. The resulting nitronates were reduced with hydrogen at 160 psi in the presence of platinum oxide to afford enantiomerically enriched pyrrolidines (both as the free base and N-protected derivatives) in good yields. A series of 3-substituted pyrrolidines (71-97% ee) were prepared, as well as (3S,4R)-4-methyl-3-phenyl-N-(p-tolylsulfonyl)pyrrolidine (92% ee) and (3S,4S)-3,4-diphenylpyrrolidine (99% ee). The chiral auxiliaries can be recovered in nearly quantitative yields after hydrogenation.

Original languageEnglish (US)
Pages (from-to)3221-3235
Number of pages15
JournalJournal of Organic Chemistry
Volume60
Issue number10
DOIs
StatePublished - May 1 1995

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Pyrrolidines
Cycloaddition
Lewis Acids
Hydrogenation
Hydrogen
Derivatives

ASJC Scopus subject areas

  • Organic Chemistry

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Asymmetric Nitroalkene [4 + 2] Cycloadditions : Enantioselective Synthesis of 3-Substituted and 3,4-Disubstituted Pyrrolidines. / Denmark, Scott E.; Marcin, Lawrence R.

In: Journal of Organic Chemistry, Vol. 60, No. 10, 01.05.1995, p. 3221-3235.

Research output: Contribution to journalArticle

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abstract = "2-Substituted 1-nitroalkenes undergo highly diastereoselective, Lewis-acid-promoted, [4 + 2] cycloaddition with chiral vinyl ethers derived from (R)-2,2-diphenylcyclopentanol and (1R,2S)-2-phenylcyclohexanol to afford cyclic nitronates in high yields. The resulting nitronates were reduced with hydrogen at 160 psi in the presence of platinum oxide to afford enantiomerically enriched pyrrolidines (both as the free base and N-protected derivatives) in good yields. A series of 3-substituted pyrrolidines (71-97{\%} ee) were prepared, as well as (3S,4R)-4-methyl-3-phenyl-N-(p-tolylsulfonyl)pyrrolidine (92{\%} ee) and (3S,4S)-3,4-diphenylpyrrolidine (99{\%} ee). The chiral auxiliaries can be recovered in nearly quantitative yields after hydrogenation.",
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N2 - 2-Substituted 1-nitroalkenes undergo highly diastereoselective, Lewis-acid-promoted, [4 + 2] cycloaddition with chiral vinyl ethers derived from (R)-2,2-diphenylcyclopentanol and (1R,2S)-2-phenylcyclohexanol to afford cyclic nitronates in high yields. The resulting nitronates were reduced with hydrogen at 160 psi in the presence of platinum oxide to afford enantiomerically enriched pyrrolidines (both as the free base and N-protected derivatives) in good yields. A series of 3-substituted pyrrolidines (71-97% ee) were prepared, as well as (3S,4R)-4-methyl-3-phenyl-N-(p-tolylsulfonyl)pyrrolidine (92% ee) and (3S,4S)-3,4-diphenylpyrrolidine (99% ee). The chiral auxiliaries can be recovered in nearly quantitative yields after hydrogenation.

AB - 2-Substituted 1-nitroalkenes undergo highly diastereoselective, Lewis-acid-promoted, [4 + 2] cycloaddition with chiral vinyl ethers derived from (R)-2,2-diphenylcyclopentanol and (1R,2S)-2-phenylcyclohexanol to afford cyclic nitronates in high yields. The resulting nitronates were reduced with hydrogen at 160 psi in the presence of platinum oxide to afford enantiomerically enriched pyrrolidines (both as the free base and N-protected derivatives) in good yields. A series of 3-substituted pyrrolidines (71-97% ee) were prepared, as well as (3S,4R)-4-methyl-3-phenyl-N-(p-tolylsulfonyl)pyrrolidine (92% ee) and (3S,4S)-3,4-diphenylpyrrolidine (99% ee). The chiral auxiliaries can be recovered in nearly quantitative yields after hydrogenation.

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