Isothiourea-mediated asymmetric functionalization of 3-alkenoic acids

Louis C. Morrill; Samuel M. Smith; Alexandra M. Z. Slawin; Andrew D. Smith

doi:10.1021/jo402591v

Isothiourea-mediated asymmetric functionalization of 3-alkenoic acids

Louis C. Morrill, Samuel M. Smith, Alexandra M. Z. Slawin, Andrew D. Smith^*

^*Corresponding author for this work

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

Abstract

Isothiourea HBTM-2.1 promotes the catalytic asymmetric alpha-functionalization of 3-alkenoic acids through formal [2 + 2] cycloadditions with N-tosyl aldimines and formal [4 + 2] cycloadditions with either 4-aryltrifluoromethyl enones or N-aryl-N-aroyl diazenes, providing useful synthetic building blocks in good yield and with excellent enantiocontrol (up to >99% ee). Stereodefined products are amenable to further synthetic elaboration through manipulation of the olefinic functionality.

Original language	English
Pages (from-to)	1640-1655
Number of pages	16
Journal	The Journal of Organic Chemistry
Volume	79
Issue number	4
Early online date	5 Feb 2014
DOIs	https://doi.org/10.1021/jo402591v
Publication status	Published - 21 Feb 2014

Keywords

Bicyclic-Beta-Lactones
Enantioselective Gamma-Amination
Carbonylative 2+2 Cycloaddition
Catalyzed Aldol-Lactonization
Promoted Bis-Cyclizations
Acyl Transfer Catalyst
Delta-Lactones
Dyotropic Rearrangements
Efficient Synthesis
Ncal Reactions

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10.1021/jo402591v

Slawin_2014_JOC_Isothiourea2_AM
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, copyright © 2014 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see To access the final edited and published work see http://dx.doi.org/10.1021/jo402591v
Accepted author manuscript, 1.5 MB

Cite this

@article{62ce62941e1243719686a94fa6e04641,

title = "Isothiourea-mediated asymmetric functionalization of 3-alkenoic acids",

abstract = "Isothiourea HBTM-2.1 promotes the catalytic asymmetric alpha-functionalization of 3-alkenoic acids through formal [2 + 2] cycloadditions with N-tosyl aldimines and formal [4 + 2] cycloadditions with either 4-aryltrifluoromethyl enones or N-aryl-N-aroyl diazenes, providing useful synthetic building blocks in good yield and with excellent enantiocontrol (up to >99\% ee). Stereodefined products are amenable to further synthetic elaboration through manipulation of the olefinic functionality.",

keywords = "Bicyclic-Beta-Lactones, Enantioselective Gamma-Amination, Carbonylative 2+2 Cycloaddition, Catalyzed Aldol-Lactonization, Promoted Bis-Cyclizations, Acyl Transfer Catalyst, Delta-Lactones, Dyotropic Rearrangements, Efficient Synthesis, Ncal Reactions",

author = "Morrill, \{Louis C.\} and Smith, \{Samuel M.\} and Slawin, \{Alexandra M. Z.\} and Smith, \{Andrew D.\}",

note = "This work is supported by funding from the Carnegie Trust for the Universities of Scotland (L.C.M.) and the European Research Council under the European Union{\textquoteright}s Seventh Framework Programme (FP7/2007-2013)/ERC Grant Agreement No. 279850. ",

year = "2014",

month = feb,

day = "21",

doi = "10.1021/jo402591v",

language = "English",

volume = "79",

pages = "1640--1655",

journal = "The Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society (ACS)",

number = "4",

}

TY - JOUR

T1 - Isothiourea-mediated asymmetric functionalization of 3-alkenoic acids

AU - Morrill, Louis C.

AU - Smith, Samuel M.

AU - Slawin, Alexandra M. Z.

AU - Smith, Andrew D.

N1 - This work is supported by funding from the Carnegie Trust for the Universities of Scotland (L.C.M.) and the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013)/ERC Grant Agreement No. 279850.

PY - 2014/2/21

Y1 - 2014/2/21

N2 - Isothiourea HBTM-2.1 promotes the catalytic asymmetric alpha-functionalization of 3-alkenoic acids through formal [2 + 2] cycloadditions with N-tosyl aldimines and formal [4 + 2] cycloadditions with either 4-aryltrifluoromethyl enones or N-aryl-N-aroyl diazenes, providing useful synthetic building blocks in good yield and with excellent enantiocontrol (up to >99% ee). Stereodefined products are amenable to further synthetic elaboration through manipulation of the olefinic functionality.

AB - Isothiourea HBTM-2.1 promotes the catalytic asymmetric alpha-functionalization of 3-alkenoic acids through formal [2 + 2] cycloadditions with N-tosyl aldimines and formal [4 + 2] cycloadditions with either 4-aryltrifluoromethyl enones or N-aryl-N-aroyl diazenes, providing useful synthetic building blocks in good yield and with excellent enantiocontrol (up to >99% ee). Stereodefined products are amenable to further synthetic elaboration through manipulation of the olefinic functionality.

KW - Bicyclic-Beta-Lactones

KW - Enantioselective Gamma-Amination

KW - Carbonylative 2+2 Cycloaddition

KW - Catalyzed Aldol-Lactonization

KW - Promoted Bis-Cyclizations

KW - Acyl Transfer Catalyst

KW - Delta-Lactones

KW - Dyotropic Rearrangements

KW - Efficient Synthesis

KW - Ncal Reactions

UR - https://www.scopus.com/pages/publications/84894557755

U2 - 10.1021/jo402591v

DO - 10.1021/jo402591v

M3 - Article

SN - 0022-3263

VL - 79

SP - 1640

EP - 1655

JO - The Journal of Organic Chemistry

JF - The Journal of Organic Chemistry

IS - 4

ER -

Isothiourea-mediated asymmetric functionalization of 3-alkenoic acids

Abstract

Keywords

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RS Uni Research Fellowship Renewal 2010: University Research Fellowship - Cabranes ans Lewis Bases as Organocatalysts Synthetic Applications

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Isothiourea-mediated asymmetric functionalization of 3-alkenoic acids

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Projects

RS Uni Research Fellowship Renewal 2010: University Research Fellowship - Cabranes ans Lewis Bases as Organocatalysts Synthetic Applications

Cite this