Experimental and theoretical studies on stereo- and regioselectivity in intramolecular nitrone-alkene cycloaddition of Hept-6-enoses derived from carbohydrates

Tony Kung Ming Shing, Annie W F Wong, Taketo Ikeno, Tohru Yamada

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

The effect of blocking groups and stereochemistry of the substituents on the regio- and stereoselectivity in intramolecular nitrone-alkene cycloaddition (INAC) of hept-6-enoses are reported. L-ribo-Hept-6-enose 12 and D-lyxo-hept-6-enose 15, both containing a 2,3-O-isopropylidene blocking group, and L-xylo-hept-6-enose 23 and D-arabino-hept-6-enose 30, both with a 2,3-O-trans-diacetal blocking group, were prepared from D-ribose and D-arabinose, respectively. With N-alkyl hydroxylamine, lactols 12 and 15 underwent an INAC reaction to give cis-fused isoxazolidines exclusively whereas lactols 23 and 30 gave a mixture of cis-, trans-fused isoxazolidines (cyclohexanols) and bridged isoxazolidines (cycloheptanols). With the 2,3-O-trans-diacetal protecting group, the bridged bicyclo[4.2.1]isoxazolidines (cycloheptanols), via the endo mode of INAC cyclization, were synthesized for the first time from unbranched sugar derivatives 23 and 30. The stereochemical outcomes of these reactions were rationalized on the basis of transition state energies obtained by computation. The present INAC showed trivial temperature, but significant solvent dependence. For lactols 23 and 30, performing the INAC in 2-propanol gave the best yields of fused isoxazolidines (cyclohexanols) whereas in dichloromethane afforded the best yields of bridged isoxazolidines (cycloheptanols).

Original languageEnglish
Pages (from-to)3253-3263
Number of pages11
JournalJournal of Organic Chemistry
Volume71
Issue number8
DOIs
Publication statusPublished - 2006 Apr 14

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Stereoselectivity
Regioselectivity
Cycloaddition
Alkenes
Carbohydrates
Cyclohexanols
Hydroxylamine
Stereochemistry
Arabinose
Ribose
2-Propanol
Methylene Chloride
Cyclization
Electron transitions
Sugars
Electron energy levels
nitrones
Derivatives

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Experimental and theoretical studies on stereo- and regioselectivity in intramolecular nitrone-alkene cycloaddition of Hept-6-enoses derived from carbohydrates. / Shing, Tony Kung Ming; Wong, Annie W F; Ikeno, Taketo; Yamada, Tohru.

In: Journal of Organic Chemistry, Vol. 71, No. 8, 14.04.2006, p. 3253-3263.

Research output: Contribution to journalArticle

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abstract = "The effect of blocking groups and stereochemistry of the substituents on the regio- and stereoselectivity in intramolecular nitrone-alkene cycloaddition (INAC) of hept-6-enoses are reported. L-ribo-Hept-6-enose 12 and D-lyxo-hept-6-enose 15, both containing a 2,3-O-isopropylidene blocking group, and L-xylo-hept-6-enose 23 and D-arabino-hept-6-enose 30, both with a 2,3-O-trans-diacetal blocking group, were prepared from D-ribose and D-arabinose, respectively. With N-alkyl hydroxylamine, lactols 12 and 15 underwent an INAC reaction to give cis-fused isoxazolidines exclusively whereas lactols 23 and 30 gave a mixture of cis-, trans-fused isoxazolidines (cyclohexanols) and bridged isoxazolidines (cycloheptanols). With the 2,3-O-trans-diacetal protecting group, the bridged bicyclo[4.2.1]isoxazolidines (cycloheptanols), via the endo mode of INAC cyclization, were synthesized for the first time from unbranched sugar derivatives 23 and 30. The stereochemical outcomes of these reactions were rationalized on the basis of transition state energies obtained by computation. The present INAC showed trivial temperature, but significant solvent dependence. For lactols 23 and 30, performing the INAC in 2-propanol gave the best yields of fused isoxazolidines (cyclohexanols) whereas in dichloromethane afforded the best yields of bridged isoxazolidines (cycloheptanols).",
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AB - The effect of blocking groups and stereochemistry of the substituents on the regio- and stereoselectivity in intramolecular nitrone-alkene cycloaddition (INAC) of hept-6-enoses are reported. L-ribo-Hept-6-enose 12 and D-lyxo-hept-6-enose 15, both containing a 2,3-O-isopropylidene blocking group, and L-xylo-hept-6-enose 23 and D-arabino-hept-6-enose 30, both with a 2,3-O-trans-diacetal blocking group, were prepared from D-ribose and D-arabinose, respectively. With N-alkyl hydroxylamine, lactols 12 and 15 underwent an INAC reaction to give cis-fused isoxazolidines exclusively whereas lactols 23 and 30 gave a mixture of cis-, trans-fused isoxazolidines (cyclohexanols) and bridged isoxazolidines (cycloheptanols). With the 2,3-O-trans-diacetal protecting group, the bridged bicyclo[4.2.1]isoxazolidines (cycloheptanols), via the endo mode of INAC cyclization, were synthesized for the first time from unbranched sugar derivatives 23 and 30. The stereochemical outcomes of these reactions were rationalized on the basis of transition state energies obtained by computation. The present INAC showed trivial temperature, but significant solvent dependence. For lactols 23 and 30, performing the INAC in 2-propanol gave the best yields of fused isoxazolidines (cyclohexanols) whereas in dichloromethane afforded the best yields of bridged isoxazolidines (cycloheptanols).

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