AuBr3-Catalyzed Thiooxime-to-Carbonyl Conversion: From Chiral Aliphatic Nitro Compounds to Ketones without Racemization

J. Bures; C. Isart; J. Vilarrasa

doi:10.1021/ol9017722

AuBr3-Catalyzed Thiooxime-to-Carbonyl Conversion: From Chiral Aliphatic Nitro Compounds to Ketones without Racemization

J. Bures, C. Isart, J. Vilarrasa

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Abstract

A new variant of the NO2-to-CO transformation (the Nef reaction) that occurs at room temperature under neutral conditions is uncovered. After the conversion of secondary nitroalkanes to phenylsulfenylketimines, these thiooximes are hydrolyzed quantitatively in situ, in THF-H2O at pH 7, by addition of AuBr3 (but not with other MXn!). Adducts arising from asymmetric nitro-Michael and nitro-aldol reactions afford 1,4-diketones and alpha-alkoxy ketones, respectively, with full retention of the configuration of the stereocenters a to the CHNO2/C=N-SPh/C=O groups.

Original language	English
Pages (from-to)	4414-4417
Number of pages	4
Journal	Organic Letters
Volume	11
DOIs	https://doi.org/10.1021/ol9017722
Publication status	Published - 2009

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Bures-2009-AuBr3-Catalyzed Thio

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title = "AuBr3-Catalyzed Thiooxime-to-Carbonyl Conversion: From Chiral Aliphatic Nitro Compounds to Ketones without Racemization",

abstract = "A new variant of the NO2-to-CO transformation (the Nef reaction) that occurs at room temperature under neutral conditions is uncovered. After the conversion of secondary nitroalkanes to phenylsulfenylketimines, these thiooximes are hydrolyzed quantitatively in situ, in THF-H2O at pH 7, by addition of AuBr3 (but not with other MXn!). Adducts arising from asymmetric nitro-Michael and nitro-aldol reactions afford 1,4-diketones and alpha-alkoxy ketones, respectively, with full retention of the configuration of the stereocenters a to the CHNO2/C=N-SPh/C=O groups.",

author = "J. Bures and C. Isart and J. Vilarrasa",

note = "M1 - 19 Times Cited: 0",

year = "2009",

doi = "10.1021/ol9017722",

language = "English",

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journal = "Organic Letters",

issn = "1523-7060",

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T1 - AuBr3-Catalyzed Thiooxime-to-Carbonyl Conversion: From Chiral Aliphatic Nitro Compounds to Ketones without Racemization

AU - Bures, J.

AU - Isart, C.

AU - Vilarrasa, J.

N1 - M1 - 19 Times Cited: 0

PY - 2009

Y1 - 2009

N2 - A new variant of the NO2-to-CO transformation (the Nef reaction) that occurs at room temperature under neutral conditions is uncovered. After the conversion of secondary nitroalkanes to phenylsulfenylketimines, these thiooximes are hydrolyzed quantitatively in situ, in THF-H2O at pH 7, by addition of AuBr3 (but not with other MXn!). Adducts arising from asymmetric nitro-Michael and nitro-aldol reactions afford 1,4-diketones and alpha-alkoxy ketones, respectively, with full retention of the configuration of the stereocenters a to the CHNO2/C=N-SPh/C=O groups.

AB - A new variant of the NO2-to-CO transformation (the Nef reaction) that occurs at room temperature under neutral conditions is uncovered. After the conversion of secondary nitroalkanes to phenylsulfenylketimines, these thiooximes are hydrolyzed quantitatively in situ, in THF-H2O at pH 7, by addition of AuBr3 (but not with other MXn!). Adducts arising from asymmetric nitro-Michael and nitro-aldol reactions afford 1,4-diketones and alpha-alkoxy ketones, respectively, with full retention of the configuration of the stereocenters a to the CHNO2/C=N-SPh/C=O groups.

U2 - 10.1021/ol9017722

DO - 10.1021/ol9017722

M3 - Article

SN - 1523-7060

VL - 11

SP - 4414

EP - 4417

JO - Organic Letters

JF - Organic Letters

ER -

AuBr3-Catalyzed Thiooxime-to-Carbonyl Conversion: From Chiral Aliphatic Nitro Compounds to Ketones without Racemization

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