Probing the efficiency of N-heterocyclic carbene promoted O- to C-carboxyl transfer of oxazolyl carbonates

Jennifer E. Thomson; Craig D. Campbell; Carmen Concellon; Nicolas Duguet; Kathryn Rix; Alexandra M. Z. Slawin; Andrew D. Smith

doi:10.1021/jo702720a

Probing the efficiency of N-heterocyclic carbene promoted O- to C-carboxyl transfer of oxazolyl carbonates

Jennifer E. Thomson, Craig D. Campbell, Carmen Concellon, Nicolas Duguet, Kathryn Rix, Alexandra M. Z. Slawin, Andrew D. Smith

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

66 Citations (Scopus)

Abstract

Screening of a range of azolium salts, bases and solvents for reactivity indicates that triazolinylidenes, generated in situ with KHMDS in THF, promote the Steglich rearrangement of oxazolyl carbonates with high catalytic efficiency (typical reaction time 5 min at < 1.5 mol % NHC). This protocol shows wide substrate applicability, even allowing the efficient generation of vicinal quaternary centers. An improved experimental procedure is also described that allows a simplified one-pot reaction protocol to be employed with similarly high catalytic efficiency.

Original language	English
Pages (from-to)	2784-2791
Number of pages	8
Journal	The Journal of Organic Chemistry
Volume	73
DOIs	https://doi.org/10.1021/jo702720a
Publication status	Published - 4 Apr 2008

Keywords

INTRAMOLECULAR STETTER REACTION
ALPHA-AMINO-ACIDS
KINETIC RESOLUTION
ENANTIOSELECTIVE ACYLATION
NUCLEOPHILIC CARBENES
TRANSESTERIFICATION/ACYLATION REACTIONS
ALPHA,BETA-UNSATURATED ALDEHYDES
STEREOSELECTIVE-SYNTHESIS
MULTICOMPONENT REACTIONS
LIVING POLYMERIZATION

Access to Document

10.1021/jo702720a

Cite this

@article{f0fa48daab184a2982404561fb7dccda,

title = "Probing the efficiency of N-heterocyclic carbene promoted O- to C-carboxyl transfer of oxazolyl carbonates",

abstract = "Screening of a range of azolium salts, bases and solvents for reactivity indicates that triazolinylidenes, generated in situ with KHMDS in THF, promote the Steglich rearrangement of oxazolyl carbonates with high catalytic efficiency (typical reaction time 5 min at < 1.5 mol % NHC). This protocol shows wide substrate applicability, even allowing the efficient generation of vicinal quaternary centers. An improved experimental procedure is also described that allows a simplified one-pot reaction protocol to be employed with similarly high catalytic efficiency.",

keywords = "INTRAMOLECULAR STETTER REACTION, ALPHA-AMINO-ACIDS, KINETIC RESOLUTION, ENANTIOSELECTIVE ACYLATION, NUCLEOPHILIC CARBENES, TRANSESTERIFICATION/ACYLATION REACTIONS, ALPHA,BETA-UNSATURATED ALDEHYDES, STEREOSELECTIVE-SYNTHESIS, MULTICOMPONENT REACTIONS, LIVING POLYMERIZATION",

author = "Thomson, {Jennifer E.} and Campbell, {Craig D.} and Carmen Concellon and Nicolas Duguet and Kathryn Rix and Slawin, {Alexandra M. Z.} and Smith, {Andrew D.}",

year = "2008",

month = apr,

day = "4",

doi = "10.1021/jo702720a",

language = "English",

volume = "73",

pages = "2784--2791",

journal = "The Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society (ACS)",

}

TY - JOUR

T1 - Probing the efficiency of N-heterocyclic carbene promoted O- to C-carboxyl transfer of oxazolyl carbonates

AU - Thomson, Jennifer E.

AU - Campbell, Craig D.

AU - Concellon, Carmen

AU - Duguet, Nicolas

AU - Rix, Kathryn

AU - Slawin, Alexandra M. Z.

AU - Smith, Andrew D.

PY - 2008/4/4

Y1 - 2008/4/4

N2 - Screening of a range of azolium salts, bases and solvents for reactivity indicates that triazolinylidenes, generated in situ with KHMDS in THF, promote the Steglich rearrangement of oxazolyl carbonates with high catalytic efficiency (typical reaction time 5 min at < 1.5 mol % NHC). This protocol shows wide substrate applicability, even allowing the efficient generation of vicinal quaternary centers. An improved experimental procedure is also described that allows a simplified one-pot reaction protocol to be employed with similarly high catalytic efficiency.

AB - Screening of a range of azolium salts, bases and solvents for reactivity indicates that triazolinylidenes, generated in situ with KHMDS in THF, promote the Steglich rearrangement of oxazolyl carbonates with high catalytic efficiency (typical reaction time 5 min at < 1.5 mol % NHC). This protocol shows wide substrate applicability, even allowing the efficient generation of vicinal quaternary centers. An improved experimental procedure is also described that allows a simplified one-pot reaction protocol to be employed with similarly high catalytic efficiency.

KW - INTRAMOLECULAR STETTER REACTION

KW - ALPHA-AMINO-ACIDS

KW - KINETIC RESOLUTION

KW - ENANTIOSELECTIVE ACYLATION

KW - NUCLEOPHILIC CARBENES

KW - TRANSESTERIFICATION/ACYLATION REACTIONS

KW - ALPHA,BETA-UNSATURATED ALDEHYDES

KW - STEREOSELECTIVE-SYNTHESIS

KW - MULTICOMPONENT REACTIONS

KW - LIVING POLYMERIZATION

UR - http://www.scopus.com/inward/record.url?scp=41649108271&partnerID=8YFLogxK

U2 - 10.1021/jo702720a

DO - 10.1021/jo702720a

M3 - Article

SN - 0022-3263

VL - 73

SP - 2784

EP - 2791

JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

ER -

Probing the efficiency of N-heterocyclic carbene promoted O- to C-carboxyl transfer of oxazolyl carbonates

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this