Tandem catalysis in domino olefin cross-metathesis/intramolecular oxa-conjugate cyclization: concise synthesis of 2,6-cis-substituted tetrahydropyran derivatives

Herein, we describe the concise synthesis of 2,6-cis-substituted tetrahydropyran derivatives based on a domino olefin cross-metathesis/intramolecular oxa-conjugate cyclization (CM/IOCC) reaction. We have found that the domino CM/IOCC of delta-hydroxy olefins with alpha,beta-unsaturated carbonyl comp...

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Published inOrganic & biomolecular chemistry Vol. 10; no. 40; pp. 8108 - 8112
Main Authors Fuwa, Haruhiko, Noguchi, Takuma, Noto, Kenkichi, Sasaki, Makoto
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 28.10.2012
Subjects
Alkenes - chemistry
Catalysis
Chemistry
Chemistry, Organic
Cyclization
Molecular Structure
Physical Sciences
Pyrans - chemical synthesis
Pyrans - chemistry
Science & Technology
Stereoisomerism
CASCADE REACTIONS
METATHESIS CATALYSTS
CARBONYL DERIVATIVES
FORMAL SYNTHESIS
BOND ISOMERIZATION SEQUENCE
NATURAL-PRODUCTS
ONE-POT
HYDROARYLATION SEQUENCE
RUTHENIUM
MICHAEL ADDITION
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Summary:Herein, we describe the concise synthesis of 2,6-cis-substituted tetrahydropyran derivatives based on a domino olefin cross-metathesis/intramolecular oxa-conjugate cyclization (CM/IOCC) reaction. We have found that the domino CM/IOCC of delta-hydroxy olefins with alpha,beta-unsaturated carbonyl compounds (e.g., trans-crotonaldehyde or N-acryloyl-2,5-dimethylpyrrole) could be efficiently achieved in the presence of the second-generation Hoveyda-Grubbs catalyst under elevated temperature conditions, directly affording 2,6-cis-substituted tetrahydropyrans in excellent yields with synthetically useful diastereoselectivity ("auto-tandem catalysis"). In addition, we have found that the domino CM/IOCC of delta-hydroxy olefins with alpha,beta-unsaturated carbonyl compounds could be achieved simply by performing CM in the presence of a Bronsted acid in CH2Cl2 at 25-35 degrees C, which delivered 2,6-cis-substituted tetrahydropyrans in good yields with excellent diastereoselectivity ("orthogonal-tandem catalysis"). To understand the mechanism of auto-tandem catalysis in the domino CM/IOCC reaction, we have investigated the role of ruthenium hydride complexes in the IOCC of a zeta-hydroxy alpha,beta-unsaturated ketone as a model case.
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ISSN:1477-0520
1477-0539
DOI:10.1039/c2ob26189h