Gold-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters to cis-cyclohepta-4,8-diene-fused pyrrolidines

A synthetic approach that provides access to cis-cyclohepta-4,8-diene-fused pyrrolidines efficiently through AuI-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters at a low catalyst loading of 2 mol % is reported. Starting carbonates and esters with a pendant alkyl group on the term...

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Main Authors: Sally, Berry, Stuart Neil, Chan, Philip Wai Hong, Rao, Weidong
Other Authors: School of Physical and Mathematical Sciences
Format: Article
Language:English
Published: 2014
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Online Access:https://hdl.handle.net/10356/100556
http://hdl.handle.net/10220/24142
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spelling sg-ntu-dr.10356-1005562020-03-07T12:37:17Z Gold-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters to cis-cyclohepta-4,8-diene-fused pyrrolidines Sally Berry, Stuart Neil Chan, Philip Wai Hong Rao, Weidong School of Physical and Mathematical Sciences DRNTU::Science::Physics::Atomic physics::Solid state physics A synthetic approach that provides access to cis-cyclohepta-4,8-diene-fused pyrrolidines efficiently through AuI-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters at a low catalyst loading of 2 mol % is reported. Starting carbonates and esters with a pendant alkyl group on the terminal alkenyl carbon center were found to favor tandem 1,2-acyloxy migration/cyclopropanation followed by Cope rearrangement of the resulting cis-3-azabicyclo[3.1.0]hexane intermediate. On the other hand, substrates containing a terminal diene or starting materials in which the distal alkene moiety bears a phenyl substituent were observed to undergo competitive but reversible 1,3-acyloxy migration prior to the nitrogen-containing bicyclic ring formation. The delineated reaction mechanism also provides experimental evidence for the reversible interconversion between the oft-proposed organogold intermediates obtained in this step of the tandem process. 2014-10-29T00:57:22Z 2019-12-06T20:24:25Z 2014-10-29T00:57:22Z 2019-12-06T20:24:25Z 2014 2014 Journal Article Rao, W., Sally, Berry, S. N., & Chan, P. W. H. (2014). Gold-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters to cis-cyclohepta-4,8-diene-fused pyrrolidines. Chemistry - A European journal, 20(41), 13174-13180. 0947-6539 https://hdl.handle.net/10356/100556 http://hdl.handle.net/10220/24142 10.1002/chem.201402500 en Chemistry - a European journal © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
institution Nanyang Technological University
building NTU Library
country Singapore
collection DR-NTU
language English
topic DRNTU::Science::Physics::Atomic physics::Solid state physics
spellingShingle DRNTU::Science::Physics::Atomic physics::Solid state physics
Sally
Berry, Stuart Neil
Chan, Philip Wai Hong
Rao, Weidong
Gold-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters to cis-cyclohepta-4,8-diene-fused pyrrolidines
description A synthetic approach that provides access to cis-cyclohepta-4,8-diene-fused pyrrolidines efficiently through AuI-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters at a low catalyst loading of 2 mol % is reported. Starting carbonates and esters with a pendant alkyl group on the terminal alkenyl carbon center were found to favor tandem 1,2-acyloxy migration/cyclopropanation followed by Cope rearrangement of the resulting cis-3-azabicyclo[3.1.0]hexane intermediate. On the other hand, substrates containing a terminal diene or starting materials in which the distal alkene moiety bears a phenyl substituent were observed to undergo competitive but reversible 1,3-acyloxy migration prior to the nitrogen-containing bicyclic ring formation. The delineated reaction mechanism also provides experimental evidence for the reversible interconversion between the oft-proposed organogold intermediates obtained in this step of the tandem process.
author2 School of Physical and Mathematical Sciences
author_facet School of Physical and Mathematical Sciences
Sally
Berry, Stuart Neil
Chan, Philip Wai Hong
Rao, Weidong
format Article
author Sally
Berry, Stuart Neil
Chan, Philip Wai Hong
Rao, Weidong
author_sort Sally
title Gold-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters to cis-cyclohepta-4,8-diene-fused pyrrolidines
title_short Gold-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters to cis-cyclohepta-4,8-diene-fused pyrrolidines
title_full Gold-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters to cis-cyclohepta-4,8-diene-fused pyrrolidines
title_fullStr Gold-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters to cis-cyclohepta-4,8-diene-fused pyrrolidines
title_full_unstemmed Gold-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters to cis-cyclohepta-4,8-diene-fused pyrrolidines
title_sort gold-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters to cis-cyclohepta-4,8-diene-fused pyrrolidines
publishDate 2014
url https://hdl.handle.net/10356/100556
http://hdl.handle.net/10220/24142
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