Strategy for Enantio- and Diastereoselective Syntheses of All Possible Stereoisomers of 1,3-Polyol Arrays Based on a Highly Catalyst-Controlled Epoxidation of α,β-Unsaturated Morpholinyl Amides: Application to Natural Product Synthesis

Shin Ya Tosaki, Yoshihiro Horiuchi, Tetsuhiro Nemoto, Takashi Ohshima, Masakatsu Shibasaki

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47 Citations (Scopus)

Abstract

We describe a new strategy for enantio- and diastereoselective syntheses of all possible stereoisomers of 1,3-polyol arrays. This strategy relies on a highly catalyst-controlled epoxidation of α,β-unsaturated morpholinyl amides promoted by the Sm-BINOL-Ph3As=O (1:1:1) complex, followed by a conversion of morpholinyl amides into ketones and diastereoselective ketone reduction. Highly enantio- (up to >99% ee) or diastereoselective (up to >99.5:0.5) epoxidation was achieved using 5-10 mol% of the Sm complex to afford synthetically very useful, nearly optically pure α,β-epoxy morpholinyl amides. Stereoselectivity of the epoxidation was controlled by the chirality of BINOL with overwhelming inherent diastereofacial preference for the substrate. Combination with the syn- and anti-selective ketone reduction with the highly catalyst-controlled epoxidation allowed for an iterative strategy for the syntheses of all possible stereoisomers of 1,3-polyol arrays. Eight possible stereoisomers of 1,3,5,7-tetraol arrays were synthesized with high to excellent stereoselectivity. Moreover, the efficiency of the present strategy was successfully demonstrated by enantioselective syntheses of several 1,3-polyol/α-pyrone natural products, for example, cryptocaryolone diacetate.

Original languageEnglish
Pages (from-to)1527-1544
Number of pages18
JournalChemistry - A European Journal
Volume10
Issue number6
DOIs
Publication statusPublished - Apr 19 2004

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Stereoisomerism
Epoxidation
Polyols
Biological Products
Amides
Ketones
Stereoselectivity
Catalysts
Pyrones
Chirality
polyol
Substrates
naphthol BINOL

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

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title = "Strategy for Enantio- and Diastereoselective Syntheses of All Possible Stereoisomers of 1,3-Polyol Arrays Based on a Highly Catalyst-Controlled Epoxidation of α,β-Unsaturated Morpholinyl Amides: Application to Natural Product Synthesis",
abstract = "We describe a new strategy for enantio- and diastereoselective syntheses of all possible stereoisomers of 1,3-polyol arrays. This strategy relies on a highly catalyst-controlled epoxidation of α,β-unsaturated morpholinyl amides promoted by the Sm-BINOL-Ph3As=O (1:1:1) complex, followed by a conversion of morpholinyl amides into ketones and diastereoselective ketone reduction. Highly enantio- (up to >99{\%} ee) or diastereoselective (up to >99.5:0.5) epoxidation was achieved using 5-10 mol{\%} of the Sm complex to afford synthetically very useful, nearly optically pure α,β-epoxy morpholinyl amides. Stereoselectivity of the epoxidation was controlled by the chirality of BINOL with overwhelming inherent diastereofacial preference for the substrate. Combination with the syn- and anti-selective ketone reduction with the highly catalyst-controlled epoxidation allowed for an iterative strategy for the syntheses of all possible stereoisomers of 1,3-polyol arrays. Eight possible stereoisomers of 1,3,5,7-tetraol arrays were synthesized with high to excellent stereoselectivity. Moreover, the efficiency of the present strategy was successfully demonstrated by enantioselective syntheses of several 1,3-polyol/α-pyrone natural products, for example, cryptocaryolone diacetate.",
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T2 - Application to Natural Product Synthesis

AU - Tosaki, Shin Ya

AU - Horiuchi, Yoshihiro

AU - Nemoto, Tetsuhiro

AU - Ohshima, Takashi

AU - Shibasaki, Masakatsu

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N2 - We describe a new strategy for enantio- and diastereoselective syntheses of all possible stereoisomers of 1,3-polyol arrays. This strategy relies on a highly catalyst-controlled epoxidation of α,β-unsaturated morpholinyl amides promoted by the Sm-BINOL-Ph3As=O (1:1:1) complex, followed by a conversion of morpholinyl amides into ketones and diastereoselective ketone reduction. Highly enantio- (up to >99% ee) or diastereoselective (up to >99.5:0.5) epoxidation was achieved using 5-10 mol% of the Sm complex to afford synthetically very useful, nearly optically pure α,β-epoxy morpholinyl amides. Stereoselectivity of the epoxidation was controlled by the chirality of BINOL with overwhelming inherent diastereofacial preference for the substrate. Combination with the syn- and anti-selective ketone reduction with the highly catalyst-controlled epoxidation allowed for an iterative strategy for the syntheses of all possible stereoisomers of 1,3-polyol arrays. Eight possible stereoisomers of 1,3,5,7-tetraol arrays were synthesized with high to excellent stereoselectivity. Moreover, the efficiency of the present strategy was successfully demonstrated by enantioselective syntheses of several 1,3-polyol/α-pyrone natural products, for example, cryptocaryolone diacetate.

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