Highly diastereoselective allylation and reduction of chiral camphor-derived α-ketoamides

Neelesh A. Kulkarni; Shy Guey Wang; Li Chen Lee; Huei Ru Tsai; Uppala Venkatesham; Kwunmin Chen

doi:10.1016/j.tetasy.2006.01.011

Highly diastereoselective allylation and reduction of chiral camphor-derived α-ketoamides

Neelesh A. Kulkarni, Shy Guey Wang, Li Chen Lee, Huei Ru Tsai, Uppala Venkatesham, Kwunmin Chen

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

8 Citations (Scopus)

Abstract

The diastereoselective allylation and reduction of camphor-derived α-ketoamides to give optically enriched α-hydroxyl amides with high to excellent stereoselectivities are described. Allylation was carried out using allyltributylstannane in the presence of a stoichiometric amount of a Lewis acid to afford the desired homoallylic alcohols in relatively high chemical yields (up to 98%) and stereoselectivities (up to 98% de). Diastereoselective reductions were performed with the relatively bulky hydride K-Selectride at -78°C to give the corresponding α-hydroxy amides in excellent chemical yields (up to 98%) and stereoselectivities (up to 98% de). The absolute configuration of the new stereogenic center of the major diastereomer was established by X-ray crystallographic analysis. Finally, stereochemical induction and the Lewis acid dependent reversal of stereoselectivity is described.

Original language	English
Pages (from-to)	336-346
Number of pages	11
Journal	Tetrahedron Asymmetry
Volume	17
Issue number	3
DOIs	https://doi.org/10.1016/j.tetasy.2006.01.011
Publication status	Published - 2006 Feb 6

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{962fe44a6b204defb4ed29a1728ac3c9,

title = "Highly diastereoselective allylation and reduction of chiral camphor-derived α-ketoamides",

abstract = "The diastereoselective allylation and reduction of camphor-derived α-ketoamides to give optically enriched α-hydroxyl amides with high to excellent stereoselectivities are described. Allylation was carried out using allyltributylstannane in the presence of a stoichiometric amount of a Lewis acid to afford the desired homoallylic alcohols in relatively high chemical yields (up to 98%) and stereoselectivities (up to 98% de). Diastereoselective reductions were performed with the relatively bulky hydride K-Selectride at -78°C to give the corresponding α-hydroxy amides in excellent chemical yields (up to 98%) and stereoselectivities (up to 98% de). The absolute configuration of the new stereogenic center of the major diastereomer was established by X-ray crystallographic analysis. Finally, stereochemical induction and the Lewis acid dependent reversal of stereoselectivity is described.",

author = "Kulkarni, {Neelesh A.} and Wang, {Shy Guey} and Lee, {Li Chen} and Tsai, {Huei Ru} and Uppala Venkatesham and Kwunmin Chen",

note = "Funding Information: This work was supported by the National Science Council of the Republic of China (NSC 94-2113-M-003-003) and National Taiwan Normal University (ORD 93-C). Our gratitude is expressed to the Academic Paper Editing Clinic, NTNU. The collection and processing of the X-ray crystal data by National Taiwan Normal University is gratefully acknowledged. ",

year = "2006",

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doi = "10.1016/j.tetasy.2006.01.011",

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AU - Kulkarni, Neelesh A.

AU - Wang, Shy Guey

AU - Lee, Li Chen

AU - Tsai, Huei Ru

AU - Venkatesham, Uppala

AU - Chen, Kwunmin

N1 - Funding Information: This work was supported by the National Science Council of the Republic of China (NSC 94-2113-M-003-003) and National Taiwan Normal University (ORD 93-C). Our gratitude is expressed to the Academic Paper Editing Clinic, NTNU. The collection and processing of the X-ray crystal data by National Taiwan Normal University is gratefully acknowledged.

PY - 2006/2/6

Y1 - 2006/2/6

N2 - The diastereoselective allylation and reduction of camphor-derived α-ketoamides to give optically enriched α-hydroxyl amides with high to excellent stereoselectivities are described. Allylation was carried out using allyltributylstannane in the presence of a stoichiometric amount of a Lewis acid to afford the desired homoallylic alcohols in relatively high chemical yields (up to 98%) and stereoselectivities (up to 98% de). Diastereoselective reductions were performed with the relatively bulky hydride K-Selectride at -78°C to give the corresponding α-hydroxy amides in excellent chemical yields (up to 98%) and stereoselectivities (up to 98% de). The absolute configuration of the new stereogenic center of the major diastereomer was established by X-ray crystallographic analysis. Finally, stereochemical induction and the Lewis acid dependent reversal of stereoselectivity is described.

AB - The diastereoselective allylation and reduction of camphor-derived α-ketoamides to give optically enriched α-hydroxyl amides with high to excellent stereoselectivities are described. Allylation was carried out using allyltributylstannane in the presence of a stoichiometric amount of a Lewis acid to afford the desired homoallylic alcohols in relatively high chemical yields (up to 98%) and stereoselectivities (up to 98% de). Diastereoselective reductions were performed with the relatively bulky hydride K-Selectride at -78°C to give the corresponding α-hydroxy amides in excellent chemical yields (up to 98%) and stereoselectivities (up to 98% de). The absolute configuration of the new stereogenic center of the major diastereomer was established by X-ray crystallographic analysis. Finally, stereochemical induction and the Lewis acid dependent reversal of stereoselectivity is described.

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