Use of copper(II)/diamine catalysts in the desymmetrisation of meso-diols and asymmetric Henry reactions: Comparison of (-)-sparteine and (+)-sparteine surrogates

Steven J. Canipa; Annika Stute; Peter O'Brien

doi:10.1016/j.tet.2014.06.117

Use of copper(II)/diamine catalysts in the desymmetrisation of meso-diols and asymmetric Henry reactions: Comparison of (-)-sparteine and (+)-sparteine surrogates

Steven J. Canipa, Annika Stute, Peter O'Brien^*

^*Corresponding author for this work

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

Abstract

Four new copper(II)/diamine complexes comprising some (+)-sparteine surrogates and a cyclohexane-derived diamine were prepared and evaluated as chiral catalysts in desymmetrisation of . meso-diols and asymmetric Henry reactions. Mono-benzoylation reactions generated two products with high enantioselectivity (90:10 to 97:3 er). Asymmetric Henry reactions gave nitro alcohols in 90:10 to 98:2 er. Notably, the sense of induction with the (+)-sparteine surrogates was opposite to that obtained using the copper(II)/(-)-sparteine complex. One of the nitro alcohol products was utilised in a concise synthesis of a chiral morpholine.

Original language	English
Pages (from-to)	7395-7403
Number of pages	9
Journal	Tetrahedron
Volume	70
Issue number	40
DOIs	https://doi.org/10.1016/j.tet.2014.06.117
Publication status	Published - Oct 2014

Keywords

Benzoylation
Copper(II) complexes
Diamines
Henry reaction
Morpholine

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abstract = "Four new copper(II)/diamine complexes comprising some (+)-sparteine surrogates and a cyclohexane-derived diamine were prepared and evaluated as chiral catalysts in desymmetrisation of . meso-diols and asymmetric Henry reactions. Mono-benzoylation reactions generated two products with high enantioselectivity (90:10 to 97:3 er). Asymmetric Henry reactions gave nitro alcohols in 90:10 to 98:2 er. Notably, the sense of induction with the (+)-sparteine surrogates was opposite to that obtained using the copper(II)/(-)-sparteine complex. One of the nitro alcohol products was utilised in a concise synthesis of a chiral morpholine.",

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author = "Canipa, {Steven J.} and Annika Stute and Peter O'Brien",

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T1 - Use of copper(II)/diamine catalysts in the desymmetrisation of meso-diols and asymmetric Henry reactions

T2 - Comparison of (-)-sparteine and (+)-sparteine surrogates

AU - Canipa, Steven J.

AU - Stute, Annika

AU - O'Brien, Peter

PY - 2014/10

Y1 - 2014/10

N2 - Four new copper(II)/diamine complexes comprising some (+)-sparteine surrogates and a cyclohexane-derived diamine were prepared and evaluated as chiral catalysts in desymmetrisation of . meso-diols and asymmetric Henry reactions. Mono-benzoylation reactions generated two products with high enantioselectivity (90:10 to 97:3 er). Asymmetric Henry reactions gave nitro alcohols in 90:10 to 98:2 er. Notably, the sense of induction with the (+)-sparteine surrogates was opposite to that obtained using the copper(II)/(-)-sparteine complex. One of the nitro alcohol products was utilised in a concise synthesis of a chiral morpholine.

AB - Four new copper(II)/diamine complexes comprising some (+)-sparteine surrogates and a cyclohexane-derived diamine were prepared and evaluated as chiral catalysts in desymmetrisation of . meso-diols and asymmetric Henry reactions. Mono-benzoylation reactions generated two products with high enantioselectivity (90:10 to 97:3 er). Asymmetric Henry reactions gave nitro alcohols in 90:10 to 98:2 er. Notably, the sense of induction with the (+)-sparteine surrogates was opposite to that obtained using the copper(II)/(-)-sparteine complex. One of the nitro alcohol products was utilised in a concise synthesis of a chiral morpholine.

KW - Benzoylation

KW - Copper(II) complexes

KW - Diamines

KW - Henry reaction

KW - Morpholine

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DO - 10.1016/j.tet.2014.06.117

M3 - Article

SN - 0040-4020

VL - 70

SP - 7395

EP - 7403

JO - Tetrahedron

JF - Tetrahedron

IS - 40

ER -

Use of copper(II)/diamine catalysts in the desymmetrisation of meso-diols and asymmetric Henry reactions: Comparison of (-)-sparteine and (+)-sparteine surrogates

Abstract

Keywords

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