Ketone homologation to produce alpha-methoxyketones: application to conduritol synthesis

N  Phillipson; M S  Anson; J G  Montana; R J K  Taylor

Ketone homologation to produce alpha-methoxyketones: application to conduritol synthesis

N Phillipson, M S Anson, J G Montana, R J K Taylor

Chemistry

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

Abstract

The scope of Trost's sulfone homologation procedure for the conversion of ketones into their alpha-methoxylated higher homologues has been dramatically expanded. The use of zirconium (or hafnium) tetrachloride in the hydroxy sulfone rearrangement step gives good yields with the adducts of aryl alkyl ketones, dialkyl ketones and cycloalkanones, and the rearrangement occurs with total regioselectivity. Mechanistic observations are presented which account for the formation of a-hydroxy aldehydes as byproducts and which indicate an efficient method for their preparation. Application of the homologation methodology to the stereoselective synthesis of dihydroconduritols is described.

Original language	English
Pages (from-to)	2821-2829
Number of pages	9
Journal	Journal of the Chemical Society-Perkin Transactions 1
Issue number	19
Publication status	Published - 7 Oct 1997

Keywords

RING EXPANSION
ZIRCONIUM TETRACHLORIDE
ALKOXY
REARRANGEMENTS
DERIVATIVES
ALDEHYDES
LACTONES
ANALOGS

Cite this

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title = "Ketone homologation to produce alpha-methoxyketones: application to conduritol synthesis",

abstract = "The scope of Trost's sulfone homologation procedure for the conversion of ketones into their alpha-methoxylated higher homologues has been dramatically expanded. The use of zirconium (or hafnium) tetrachloride in the hydroxy sulfone rearrangement step gives good yields with the adducts of aryl alkyl ketones, dialkyl ketones and cycloalkanones, and the rearrangement occurs with total regioselectivity. Mechanistic observations are presented which account for the formation of a-hydroxy aldehydes as byproducts and which indicate an efficient method for their preparation. Application of the homologation methodology to the stereoselective synthesis of dihydroconduritols is described.",

keywords = "RING EXPANSION, ZIRCONIUM TETRACHLORIDE, ALKOXY, REARRANGEMENTS, DERIVATIVES, ALDEHYDES, LACTONES, ANALOGS",

author = "N Phillipson and Anson, {M S} and Montana, {J G} and Taylor, {R J K}",

year = "1997",

month = oct,

day = "7",

language = "English",

pages = "2821--2829",

journal = "Journal of the Chemical Society-Perkin Transactions 1",

issn = "0300-922X",

publisher = "Chemical Society",

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TY - JOUR

T1 - Ketone homologation to produce alpha-methoxyketones: application to conduritol synthesis

AU - Phillipson, N

AU - Anson, M S

AU - Montana, J G

AU - Taylor, R J K

PY - 1997/10/7

Y1 - 1997/10/7

N2 - The scope of Trost's sulfone homologation procedure for the conversion of ketones into their alpha-methoxylated higher homologues has been dramatically expanded. The use of zirconium (or hafnium) tetrachloride in the hydroxy sulfone rearrangement step gives good yields with the adducts of aryl alkyl ketones, dialkyl ketones and cycloalkanones, and the rearrangement occurs with total regioselectivity. Mechanistic observations are presented which account for the formation of a-hydroxy aldehydes as byproducts and which indicate an efficient method for their preparation. Application of the homologation methodology to the stereoselective synthesis of dihydroconduritols is described.

AB - The scope of Trost's sulfone homologation procedure for the conversion of ketones into their alpha-methoxylated higher homologues has been dramatically expanded. The use of zirconium (or hafnium) tetrachloride in the hydroxy sulfone rearrangement step gives good yields with the adducts of aryl alkyl ketones, dialkyl ketones and cycloalkanones, and the rearrangement occurs with total regioselectivity. Mechanistic observations are presented which account for the formation of a-hydroxy aldehydes as byproducts and which indicate an efficient method for their preparation. Application of the homologation methodology to the stereoselective synthesis of dihydroconduritols is described.

KW - RING EXPANSION

KW - ZIRCONIUM TETRACHLORIDE

KW - ALKOXY

KW - REARRANGEMENTS

KW - DERIVATIVES

KW - ALDEHYDES

KW - LACTONES

KW - ANALOGS

M3 - Article

SN - 0300-922X

SP - 2821

EP - 2829

JO - Journal of the Chemical Society-Perkin Transactions 1

JF - Journal of the Chemical Society-Perkin Transactions 1

IS - 19

ER -