Enantioselective NHC-catalyzed redox [4+2]-hetero-Diels-Alder reactions using α,β-unsaturated trichloromethyl ketones as amide equivalents

Nassilia Attaba; James Edward Taylor; Alexandra Martha Zoya Slawin; Andrew David Smith

doi:10.1021/acs.joc.5b01820

Enantioselective NHC-catalyzed redox [4+2]-hetero-Diels-Alder reactions using α,β-unsaturated trichloromethyl ketones as amide equivalents

Nassilia Attaba, James Edward Taylor, Alexandra Martha Zoya Slawin, Andrew David Smith

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

34 Citations (Scopus)

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Abstract

α,β-Unsaturated trichloromethyl ketones are suitable α,β-unsaturated amide and ester equivalents in N-heterocyclic carbene (NHC)-catalyzed redox hetero-Diels-Alder reactions with azolium enolates generated from α-aroyloxyaldehydes. The initially formed syn-dihydropyranone products can be isolated, or can undergo ring-opening with benzylamine followed by aminolysis of the resulting CCl₃ ketone to form a range of diamides with high diastereo- and enantioselectivity (up to >95:5 dr and >99% ee).

Original language	English
Pages (from-to)	9728–9739
Journal	The Journal of Organic Chemistry
Volume	80
Issue number	19
Early online date	5 Sept 2015
DOIs	https://doi.org/10.1021/acs.joc.5b01820
Publication status	Published - 2 Oct 2015

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10.1021/acs.joc.5b01820

Smith_2015_JOC_Enantioselective_AM
Copyright © 2015 American Chemical Society. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://dx.doi.org/10.1021/acs.joc.5b01820
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@article{b9c18a0753304b3a91b483379e1b67fa,

title = "Enantioselective NHC-catalyzed redox [4+2]-hetero-Diels-Alder reactions using α,β-unsaturated trichloromethyl ketones as amide equivalents",

abstract = "α,β-Unsaturated trichloromethyl ketones are suitable α,β-unsaturated amide and ester equivalents in N-heterocyclic carbene (NHC)-catalyzed redox hetero-Diels-Alder reactions with azolium enolates generated from α-aroyloxyaldehydes. The initially formed syn-dihydropyranone products can be isolated, or can undergo ring-opening with benzylamine followed by aminolysis of the resulting CCl3 ketone to form a range of diamides with high diastereo- and enantioselectivity (up to >95:5 dr and >99% ee).",

author = "Nassilia Attaba and Taylor, {James Edward} and Slawin, {Alexandra Martha Zoya} and Smith, {Andrew David}",

note = "The authors thank the Royal Society for a University Research Fellowship (A.D.S.) and the European Research Council under the European Union{\textquoteright}s Seventh Framework Programme (FP7/2007-2013) ERC Grant Agreement No. 279850 (N.A. and J.E.T.). ",

year = "2015",

month = oct,

day = "2",

doi = "10.1021/acs.joc.5b01820",

language = "English",

volume = "80",

pages = "9728–9739",

journal = "The Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society (ACS)",

number = "19",

}

Enantioselective NHC-catalyzed redox [4+2]-hetero-Diels-Alder reactions using α,β-unsaturated trichloromethyl ketones as amide equivalents. / Attaba, Nassilia; Taylor, James Edward; Slawin, Alexandra Martha Zoya et al.
In: The Journal of Organic Chemistry, Vol. 80, No. 19, 02.10.2015, p. 9728–9739.

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

TY - JOUR

T1 - Enantioselective NHC-catalyzed redox [4+2]-hetero-Diels-Alder reactions using α,β-unsaturated trichloromethyl ketones as amide equivalents

AU - Attaba, Nassilia

AU - Taylor, James Edward

AU - Slawin, Alexandra Martha Zoya

AU - Smith, Andrew David

N1 - The authors thank the Royal Society for a University Research Fellowship (A.D.S.) and the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013) ERC Grant Agreement No. 279850 (N.A. and J.E.T.).

PY - 2015/10/2

Y1 - 2015/10/2

N2 - α,β-Unsaturated trichloromethyl ketones are suitable α,β-unsaturated amide and ester equivalents in N-heterocyclic carbene (NHC)-catalyzed redox hetero-Diels-Alder reactions with azolium enolates generated from α-aroyloxyaldehydes. The initially formed syn-dihydropyranone products can be isolated, or can undergo ring-opening with benzylamine followed by aminolysis of the resulting CCl3 ketone to form a range of diamides with high diastereo- and enantioselectivity (up to >95:5 dr and >99% ee).

AB - α,β-Unsaturated trichloromethyl ketones are suitable α,β-unsaturated amide and ester equivalents in N-heterocyclic carbene (NHC)-catalyzed redox hetero-Diels-Alder reactions with azolium enolates generated from α-aroyloxyaldehydes. The initially formed syn-dihydropyranone products can be isolated, or can undergo ring-opening with benzylamine followed by aminolysis of the resulting CCl3 ketone to form a range of diamides with high diastereo- and enantioselectivity (up to >95:5 dr and >99% ee).

UR - http://pubsdc3.acs.org/doi/suppl/10.1021/acs.joc.5b01820

U2 - 10.1021/acs.joc.5b01820

DO - 10.1021/acs.joc.5b01820

M3 - Article

SN - 0022-3263

VL - 80

SP - 9728

EP - 9739

JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

IS - 19

ER -

Enantioselective NHC-catalyzed redox [4+2]-hetero-Diels-Alder reactions using α,β-unsaturated trichloromethyl ketones as amide equivalents

Abstract

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