Structure-enantioselectivity effects in 3,4-dihydropyrimido[2,1-b]-benzothiazole-based isothioureas as enantioselective acylation catalysts

Dorine Belmessieri; Caroline Joannesse; Philip A. Woods; Callum MacGregor; Caroline Jones; Craig D. Campbell; Craig P. Johnston; Nicolas Duguet; Carmen Concellon; Ryan A. Bragg; Andrew D. Smith

doi:10.1039/c0ob00515k

Structure-enantioselectivity effects in 3,4-dihydropyrimido[2,1-b]-benzothiazole-based isothioureas as enantioselective acylation catalysts

Dorine Belmessieri, Caroline Joannesse, Philip A. Woods, Callum MacGregor, Caroline Jones, Craig D. Campbell, Craig P. Johnston, Nicolas Duguet, Carmen Concellon, Ryan A. Bragg, Andrew D. Smith

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

Abstract

The catalytic activity and enantioselectivity in the kinetic resolution of (+/-)-1-naphthylethanol with a range of structurally related 3,4-dihydropyrimido[2,1-b]benzothiazole-based catalysts is examined. Of the isothiourea catalysts screened, (2S,3R)-2-phenyl-3-isopropyl substitution proved optimal, giving good levels of selectivity in the kinetic resolution of a number of secondary alcohols (S values up to > 100 at similar to 50% conversion). Low catalyst loadings (0.10-0.25 mol%) of the optimal isothiourea can be used to generate enantiopure alcohols (>99% ee) in good yields.

Original language	English
Pages (from-to)	559-570
Number of pages	12
Journal	Organic & Biomolecular Chemistry
Volume	9
Issue number	2
DOIs	https://doi.org/10.1039/c0ob00515k
Publication status	Published - 2011

Keywords

NONENZYMATIC KINETIC RESOLUTION
N-HETEROCYCLIC CARBENES
ACYL TRANSFER CATALYSTS
CHIRAL PHOSPHINE CATALYSTS
C-CARBOXYL TRANSFER
ASYMMETRIC ACYLATION
SECONDARY ALCOHOLS
SEC-ALCOHOLS
NUCLEOPHILIC CATALYSIS
PROPARGYLIC ALCOHOLS

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10.1039/c0ob00515k

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Belmessieri, D., Joannesse, C., Woods, P. A., MacGregor, C., Jones, C., Campbell, C. D., Johnston, C. P., Duguet, N., Concellon, C., Bragg, R. A., & Smith, A. D. (2011). Structure-enantioselectivity effects in 3,4-dihydropyrimido[2,1-b]-benzothiazole-based isothioureas as enantioselective acylation catalysts. Organic & Biomolecular Chemistry, 9(2), 559-570. https://doi.org/10.1039/c0ob00515k

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title = "Structure-enantioselectivity effects in 3,4-dihydropyrimido[2,1-b]-benzothiazole-based isothioureas as enantioselective acylation catalysts",

abstract = "The catalytic activity and enantioselectivity in the kinetic resolution of (+/-)-1-naphthylethanol with a range of structurally related 3,4-dihydropyrimido[2,1-b]benzothiazole-based catalysts is examined. Of the isothiourea catalysts screened, (2S,3R)-2-phenyl-3-isopropyl substitution proved optimal, giving good levels of selectivity in the kinetic resolution of a number of secondary alcohols (S values up to > 100 at similar to 50\% conversion). Low catalyst loadings (0.10-0.25 mol\%) of the optimal isothiourea can be used to generate enantiopure alcohols (>99\% ee) in good yields.",

keywords = "NONENZYMATIC KINETIC RESOLUTION, N-HETEROCYCLIC CARBENES, ACYL TRANSFER CATALYSTS, CHIRAL PHOSPHINE CATALYSTS, C-CARBOXYL TRANSFER, ASYMMETRIC ACYLATION, SECONDARY ALCOHOLS, SEC-ALCOHOLS, NUCLEOPHILIC CATALYSIS, PROPARGYLIC ALCOHOLS",

author = "Dorine Belmessieri and Caroline Joannesse and Woods, \{Philip A.\} and Callum MacGregor and Caroline Jones and Campbell, \{Craig D.\} and Johnston, \{Craig P.\} and Nicolas Duguet and Carmen Concellon and Bragg, \{Ryan A.\} and Smith, \{Andrew D.\}",

year = "2011",

doi = "10.1039/c0ob00515k",

language = "English",

volume = "9",

pages = "559--570",

journal = "Organic \& Biomolecular Chemistry",

issn = "1477-0539",

publisher = "Royal Society of Chemistry",

number = "2",

}

Belmessieri, D, Joannesse, C, Woods, PA, MacGregor, C, Jones, C, Campbell, CD, Johnston, CP, Duguet, N, Concellon, C, Bragg, RA & Smith, AD 2011, 'Structure-enantioselectivity effects in 3,4-dihydropyrimido[2,1-b]-benzothiazole-based isothioureas as enantioselective acylation catalysts', Organic & Biomolecular Chemistry, vol. 9, no. 2, pp. 559-570. https://doi.org/10.1039/c0ob00515k

TY - JOUR

T1 - Structure-enantioselectivity effects in 3,4-dihydropyrimido[2,1-b]-benzothiazole-based isothioureas as enantioselective acylation catalysts

AU - Belmessieri, Dorine

AU - Joannesse, Caroline

AU - Woods, Philip A.

AU - MacGregor, Callum

AU - Jones, Caroline

AU - Campbell, Craig D.

AU - Johnston, Craig P.

AU - Duguet, Nicolas

AU - Concellon, Carmen

AU - Bragg, Ryan A.

AU - Smith, Andrew D.

PY - 2011

Y1 - 2011

N2 - The catalytic activity and enantioselectivity in the kinetic resolution of (+/-)-1-naphthylethanol with a range of structurally related 3,4-dihydropyrimido[2,1-b]benzothiazole-based catalysts is examined. Of the isothiourea catalysts screened, (2S,3R)-2-phenyl-3-isopropyl substitution proved optimal, giving good levels of selectivity in the kinetic resolution of a number of secondary alcohols (S values up to > 100 at similar to 50% conversion). Low catalyst loadings (0.10-0.25 mol%) of the optimal isothiourea can be used to generate enantiopure alcohols (>99% ee) in good yields.

AB - The catalytic activity and enantioselectivity in the kinetic resolution of (+/-)-1-naphthylethanol with a range of structurally related 3,4-dihydropyrimido[2,1-b]benzothiazole-based catalysts is examined. Of the isothiourea catalysts screened, (2S,3R)-2-phenyl-3-isopropyl substitution proved optimal, giving good levels of selectivity in the kinetic resolution of a number of secondary alcohols (S values up to > 100 at similar to 50% conversion). Low catalyst loadings (0.10-0.25 mol%) of the optimal isothiourea can be used to generate enantiopure alcohols (>99% ee) in good yields.

KW - NONENZYMATIC KINETIC RESOLUTION

KW - N-HETEROCYCLIC CARBENES

KW - ACYL TRANSFER CATALYSTS

KW - CHIRAL PHOSPHINE CATALYSTS

KW - C-CARBOXYL TRANSFER

KW - ASYMMETRIC ACYLATION

KW - SECONDARY ALCOHOLS

KW - SEC-ALCOHOLS

KW - NUCLEOPHILIC CATALYSIS

KW - PROPARGYLIC ALCOHOLS

UR - https://www.scopus.com/pages/publications/78650731829

U2 - 10.1039/c0ob00515k

DO - 10.1039/c0ob00515k

M3 - Article

SN - 1477-0539

VL - 9

SP - 559

EP - 570

JO - Organic & Biomolecular Chemistry

JF - Organic & Biomolecular Chemistry

IS - 2

ER -

Structure-enantioselectivity effects in 3,4-dihydropyrimido[2,1-b]-benzothiazole-based isothioureas as enantioselective acylation catalysts

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N-Heterocyclic Carbenes as Asymmetric: N-Heterocyclic Carbenes as Asymmetric Organocatalysts: Reaction Development

Applications of isothioureas in organocatalysis: kinetic resolution of secondary alcohols and intramolecular Michael addition-lactonisation

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Structure-enantioselectivity effects in 3,4-dihydropyrimido[2,1-b]-benzothiazole-based isothioureas as enantioselective acylation catalysts

Abstract

Keywords

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N-Heterocyclic Carbenes as Asymmetric: N-Heterocyclic Carbenes as Asymmetric Organocatalysts: Reaction Development

Student theses

Applications of isothioureas in organocatalysis: kinetic resolution of secondary alcohols and intramolecular Michael addition-lactonisation

Cite this