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Domino synthesis of 4-vinyl-oxazoles - 1,2-rearrangement cascades en route to siphonazole B

Paulsen, Filip LU (2014) KEMR31 20141
Department of Chemistry
Abstract
A novel tandem cyclocondensation/1,2-oxazole rearrangement cascade reaction for the synthesis of 4-vinyl oxazoles from γ-chloro-propargylamines was developed and applied towards a short modular synthesis of natural product siphonazole B. The proposed seven-step route, enabled by the use of 4-vinyl oxazoles as precursors for 4-carboxyl oxazoles, would be the shortest to date. Simply removing the cause of a known regioselectivity issue and using a 4-hydroxymethyl-oxazole as a masked 4-carboxyl-oxazole nucleophile solved the problem and enabled the key reaction – a regioselective aldol-type fragment coupling. Due to difficulties of achieving a latestage formal dehydrogenation the strategy was re-evaluated leading to a formal synthesis of... (More)
A novel tandem cyclocondensation/1,2-oxazole rearrangement cascade reaction for the synthesis of 4-vinyl oxazoles from γ-chloro-propargylamines was developed and applied towards a short modular synthesis of natural product siphonazole B. The proposed seven-step route, enabled by the use of 4-vinyl oxazoles as precursors for 4-carboxyl oxazoles, would be the shortest to date. Simply removing the cause of a known regioselectivity issue and using a 4-hydroxymethyl-oxazole as a masked 4-carboxyl-oxazole nucleophile solved the problem and enabled the key reaction – a regioselective aldol-type fragment coupling. Due to difficulties of achieving a latestage formal dehydrogenation the strategy was re-evaluated leading to a formal synthesis of siphonazole B. Studies towards achieving the last step of the total synthesis – a tandem oxidative amidation/ketone formation are currently underway. (Less)
Please use this url to cite or link to this publication:
author
Paulsen, Filip LU
supervisor
organization
course
KEMR31 20141
year
type
H2 - Master's Degree (Two Years)
subject
keywords
organisk kemi, organic chemistry
language
English
id
4647765
date added to LUP
2014-09-22 11:04:27
date last changed
2014-09-22 11:04:27
@misc{4647765,
  abstract     = {{A novel tandem cyclocondensation/1,2-oxazole rearrangement cascade reaction for the synthesis of 4-vinyl oxazoles from γ-chloro-propargylamines was developed and applied towards a short modular synthesis of natural product siphonazole B. The proposed seven-step route, enabled by the use of 4-vinyl oxazoles as precursors for 4-carboxyl oxazoles, would be the shortest to date. Simply removing the cause of a known regioselectivity issue and using a 4-hydroxymethyl-oxazole as a masked 4-carboxyl-oxazole nucleophile solved the problem and enabled the key reaction – a regioselective aldol-type fragment coupling. Due to difficulties of achieving a latestage formal dehydrogenation the strategy was re-evaluated leading to a formal synthesis of siphonazole B. Studies towards achieving the last step of the total synthesis – a tandem oxidative amidation/ketone formation are currently underway.}},
  author       = {{Paulsen, Filip}},
  language     = {{eng}},
  note         = {{Student Paper}},
  title        = {{Domino synthesis of 4-vinyl-oxazoles - 1,2-rearrangement cascades en route to siphonazole B}},
  year         = {{2014}},
}