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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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. |
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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 |
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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. |
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School of Physical and Mathematical Sciences |
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School of Physical and Mathematical Sciences Sally Berry, Stuart Neil Chan, Philip Wai Hong Rao, Weidong |
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Sally Berry, Stuart Neil Chan, Philip Wai Hong Rao, Weidong |
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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 |
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https://hdl.handle.net/10356/100556 http://hdl.handle.net/10220/24142 |
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1681043380305395712 |