Enantio- and diastereoselective access to distant stereocenters embedded within tetrahydroxanthenes: Utilizing ortho-quinone methides as reactive intermediates in asymmetric brønsted acid catalysis

Chien Chi Hsiao; Hsuan Hung Liao; Magnus Rueping

doi:10.1002/anie.201406587

Enantio- and diastereoselective access to distant stereocenters embedded within tetrahydroxanthenes: Utilizing ortho-quinone methides as reactive intermediates in asymmetric brønsted acid catalysis

Chien Chi Hsiao, Hsuan Hung Liao, Magnus Rueping^*

^*Corresponding author for this work

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

204 Scopus citations

Abstract

A protocol for the highly enantioselective synthesis of 9-substituted tetrahydroxanthenones by means of asymmetric Brønsted acid catalysis has been developed. A chiral binolbased N-triflyphosphoramide was found to promote the in situ generation of ortho-quinone methides and their subsequent reaction with 1,3-cyclohexanedione to provide the desired products with excellent enantioselectivities. In addition, a highly enantio- and diastereoselective Brønsted acid catalyzed desymmetrization of 5-monosubstituted 1,3-dicarbonyl substrates with ortho-quinone methides gives rise to valuable tetrahydroxanthenes containing two distant stereocenters.

Original language	English (US)
Pages (from-to)	13258-13263
Number of pages	6
Journal	Angewandte Chemie - International Edition
Volume	53
Issue number	48
DOIs	https://doi.org/10.1002/anie.201406587
State	Published - Nov 24 2014
Externally published	Yes

Keywords

Cyclization
Enantioselectivity
Heterocycles
Organocatalysis
Synthetic methods

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1002/anie.201406587

Cite this

@article{29b206baf6bc4f079c8f66a3ab2d3f32,

title = "Enantio- and diastereoselective access to distant stereocenters embedded within tetrahydroxanthenes: Utilizing ortho-quinone methides as reactive intermediates in asymmetric br{\o}nsted acid catalysis",

abstract = "A protocol for the highly enantioselective synthesis of 9-substituted tetrahydroxanthenones by means of asymmetric Br{\o}nsted acid catalysis has been developed. A chiral binolbased N-triflyphosphoramide was found to promote the in situ generation of ortho-quinone methides and their subsequent reaction with 1,3-cyclohexanedione to provide the desired products with excellent enantioselectivities. In addition, a highly enantio- and diastereoselective Br{\o}nsted acid catalyzed desymmetrization of 5-monosubstituted 1,3-dicarbonyl substrates with ortho-quinone methides gives rise to valuable tetrahydroxanthenes containing two distant stereocenters.",

keywords = "Cyclization, Enantioselectivity, Heterocycles, Organocatalysis, Synthetic methods",

author = "Hsiao, {Chien Chi} and Liao, {Hsuan Hung} and Magnus Rueping",

note = "Publisher Copyright: {\textcopyright} 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2014",

month = nov,

day = "24",

doi = "10.1002/anie.201406587",

language = "English (US)",

volume = "53",

pages = "13258--13263",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "Wiley",

number = "48",

}

Enantio- and diastereoselective access to distant stereocenters embedded within tetrahydroxanthenes: Utilizing ortho-quinone methides as reactive intermediates in asymmetric brønsted acid catalysis. / Hsiao, Chien Chi; Liao, Hsuan Hung; Rueping, Magnus.
In: Angewandte Chemie - International Edition, Vol. 53, No. 48, 24.11.2014, p. 13258-13263.

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

TY - JOUR

T1 - Enantio- and diastereoselective access to distant stereocenters embedded within tetrahydroxanthenes

T2 - Utilizing ortho-quinone methides as reactive intermediates in asymmetric brønsted acid catalysis

AU - Hsiao, Chien Chi

AU - Liao, Hsuan Hung

AU - Rueping, Magnus

PY - 2014/11/24

Y1 - 2014/11/24

N2 - A protocol for the highly enantioselective synthesis of 9-substituted tetrahydroxanthenones by means of asymmetric Brønsted acid catalysis has been developed. A chiral binolbased N-triflyphosphoramide was found to promote the in situ generation of ortho-quinone methides and their subsequent reaction with 1,3-cyclohexanedione to provide the desired products with excellent enantioselectivities. In addition, a highly enantio- and diastereoselective Brønsted acid catalyzed desymmetrization of 5-monosubstituted 1,3-dicarbonyl substrates with ortho-quinone methides gives rise to valuable tetrahydroxanthenes containing two distant stereocenters.

AB - A protocol for the highly enantioselective synthesis of 9-substituted tetrahydroxanthenones by means of asymmetric Brønsted acid catalysis has been developed. A chiral binolbased N-triflyphosphoramide was found to promote the in situ generation of ortho-quinone methides and their subsequent reaction with 1,3-cyclohexanedione to provide the desired products with excellent enantioselectivities. In addition, a highly enantio- and diastereoselective Brønsted acid catalyzed desymmetrization of 5-monosubstituted 1,3-dicarbonyl substrates with ortho-quinone methides gives rise to valuable tetrahydroxanthenes containing two distant stereocenters.

KW - Cyclization

KW - Enantioselectivity

KW - Heterocycles

KW - Organocatalysis

KW - Synthetic methods

UR - http://www.scopus.com/inward/record.url?scp=84915749984&partnerID=8YFLogxK

U2 - 10.1002/anie.201406587

DO - 10.1002/anie.201406587

M3 - Article

C2 - 25287936

AN - SCOPUS:84915749984

SN - 1433-7851

VL - 53

SP - 13258

EP - 13263

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 48

ER -

Enantio- and diastereoselective access to distant stereocenters embedded within tetrahydroxanthenes: Utilizing ortho-quinone methides as reactive intermediates in asymmetric brønsted acid catalysis

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this