Doubly diastereoselective [3,3]-sigmatropic aza-Claisen rearrangements

Stephen G. Davies; A. Christopher Garner; Rebecca L. Nicholson; James Osborne; Paul M. Roberts; Edward D. Savory; Andrew D. Smith; James E. Thomson

doi:10.1039/b902753j

Doubly diastereoselective [3,3]-sigmatropic aza-Claisen rearrangements

Stephen G. Davies, A. Christopher Garner, Rebecca L. Nicholson, James Osborne, Paul M. Roberts, Edward D. Savory, Andrew D. Smith, James E. Thomson

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

24 Citations (Scopus)

Abstract

The doubly diastereoselective [3,3]-sigmatropic aza-Claisen rearrangement of silylketene aminals derived from 5-substituted (3S,4E,alpha R)-1-benzyloxy-3-[N-acyl-N-(alpha-methylbenzyl) amino]pent-4-enes furnishes 2,3-disubstituted (R)-N-alpha-methylbenzyl (2S,3R,4E)-7-benzyloxyhept-4-enamides in >90% de under the "matched" control of both stereogenic centres. Rearrangement of the "mismatched" diastereomeric (3R,4E,alpha R)-substrates proceeds with low diastereoselectivity. The substrate scope of the doubly diastereoselective rearrangement of the "matched" substrates in which two new stereogenic centres are created has been delineated.

Original language	English
Pages (from-to)	2604-2611
Number of pages	8
Journal	Organic & Biomolecular Chemistry
Volume	7
Issue number	12
DOIs	https://doi.org/10.1039/b902753j
Publication status	Published - 2009

Keywords

STEREOSELECTIVE-SYNTHESIS
STEREOCHEMICAL CONTROL
ENANTIOMERICALLY PURE
ASYMMETRIC INDUCTION
ORGANIC-SYNTHESIS
CRYSTAL-STRUCTURE
AMINO-ACIDS
ACETAL
(-)-ISOIRIDOMYRMECIN
AUXILIARY

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title = "Doubly diastereoselective [3,3]-sigmatropic aza-Claisen rearrangements",

abstract = "The doubly diastereoselective [3,3]-sigmatropic aza-Claisen rearrangement of silylketene aminals derived from 5-substituted (3S,4E,alpha R)-1-benzyloxy-3-[N-acyl-N-(alpha-methylbenzyl) amino]pent-4-enes furnishes 2,3-disubstituted (R)-N-alpha-methylbenzyl (2S,3R,4E)-7-benzyloxyhept-4-enamides in >90% de under the {"}matched{"} control of both stereogenic centres. Rearrangement of the {"}mismatched{"} diastereomeric (3R,4E,alpha R)-substrates proceeds with low diastereoselectivity. The substrate scope of the doubly diastereoselective rearrangement of the {"}matched{"} substrates in which two new stereogenic centres are created has been delineated.",

keywords = "STEREOSELECTIVE-SYNTHESIS, STEREOCHEMICAL CONTROL, ENANTIOMERICALLY PURE, ASYMMETRIC INDUCTION, ORGANIC-SYNTHESIS, CRYSTAL-STRUCTURE, AMINO-ACIDS, ACETAL, (-)-ISOIRIDOMYRMECIN, AUXILIARY",

author = "Davies, {Stephen G.} and Garner, {A. Christopher} and Nicholson, {Rebecca L.} and James Osborne and Roberts, {Paul M.} and Savory, {Edward D.} and Smith, {Andrew D.} and Thomson, {James E.}",

year = "2009",

doi = "10.1039/b902753j",

language = "English",

volume = "7",

pages = "2604--2611",

journal = "Organic & Biomolecular Chemistry",

issn = "1477-0539",

publisher = "Royal Society of Chemistry",

number = "12",

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T1 - Doubly diastereoselective [3,3]-sigmatropic aza-Claisen rearrangements

AU - Davies, Stephen G.

AU - Garner, A. Christopher

AU - Nicholson, Rebecca L.

AU - Osborne, James

AU - Roberts, Paul M.

AU - Savory, Edward D.

AU - Smith, Andrew D.

AU - Thomson, James E.

PY - 2009

Y1 - 2009

N2 - The doubly diastereoselective [3,3]-sigmatropic aza-Claisen rearrangement of silylketene aminals derived from 5-substituted (3S,4E,alpha R)-1-benzyloxy-3-[N-acyl-N-(alpha-methylbenzyl) amino]pent-4-enes furnishes 2,3-disubstituted (R)-N-alpha-methylbenzyl (2S,3R,4E)-7-benzyloxyhept-4-enamides in >90% de under the "matched" control of both stereogenic centres. Rearrangement of the "mismatched" diastereomeric (3R,4E,alpha R)-substrates proceeds with low diastereoselectivity. The substrate scope of the doubly diastereoselective rearrangement of the "matched" substrates in which two new stereogenic centres are created has been delineated.

AB - The doubly diastereoselective [3,3]-sigmatropic aza-Claisen rearrangement of silylketene aminals derived from 5-substituted (3S,4E,alpha R)-1-benzyloxy-3-[N-acyl-N-(alpha-methylbenzyl) amino]pent-4-enes furnishes 2,3-disubstituted (R)-N-alpha-methylbenzyl (2S,3R,4E)-7-benzyloxyhept-4-enamides in >90% de under the "matched" control of both stereogenic centres. Rearrangement of the "mismatched" diastereomeric (3R,4E,alpha R)-substrates proceeds with low diastereoselectivity. The substrate scope of the doubly diastereoselective rearrangement of the "matched" substrates in which two new stereogenic centres are created has been delineated.

KW - STEREOSELECTIVE-SYNTHESIS

KW - STEREOCHEMICAL CONTROL

KW - ENANTIOMERICALLY PURE

KW - ASYMMETRIC INDUCTION

KW - ORGANIC-SYNTHESIS

KW - CRYSTAL-STRUCTURE

KW - AMINO-ACIDS

KW - ACETAL

KW - (-)-ISOIRIDOMYRMECIN

KW - AUXILIARY

U2 - 10.1039/b902753j

DO - 10.1039/b902753j

M3 - Article

SN - 1477-0539

VL - 7

SP - 2604

EP - 2611

JO - Organic & Biomolecular Chemistry

JF - Organic & Biomolecular Chemistry

IS - 12

ER -

Doubly diastereoselective [3,3]-sigmatropic aza-Claisen rearrangements

Abstract

Keywords

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