Gold‐Catalyzed Cycloisomerization and Diels–Alder Reaction of 1,4,9‐Dienyne Esters to 3 a,6‐Methanoisoindole Esters with Pro‐Inflammatory Cytokine Antagonist Activity

Abstract

. (2015) Gold-catalyzed cycloisomerization and Diels-Alder reaction of 1,4,9-Dienyne Esters to 3 a,6-Methanoisoindole Esters with pro-inflammatory cytokine antagonist activity. Chemistry -A European Journal, 21 (25 Copies of full items can be used for personal research or study, educational, or not-for profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher's statement:"This is the peer reviewed version of the following Susanti, Dewi, Liu, Li-Juan, Rao, Weidong, Lin, Sheng, Ma, Dik-Lung, Leung, Chung-Hang and Chan, Philip Wai Hong. (2015) Goldcatalyzed cycloisomerization and Diels-Alder reaction of 1,4,9-Dienyne Esters to 3 a,6-Methanoisoindole Esters with pro-inflammatory cytokine antagonist activity. Chemistry -A European Journal, 21 (25). pp. 9111-9118. which has been published in final form at http://dx.doi.org/10.1002/chem.201500795 . This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving." A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP URL' above for details on accessing the published version and note that access may require a subscription. Abstract: A synthetic method to prepare 3a,6-methanoisoindole esters efficiently by gold(I)-catalyzed tandem 1,2-acyloxy migration/Nazarov cyclization followed by Diels-Alder reaction of 1,4,9-dienyne esters is described. We also report the ability of one example to inhibit binding of tumor necrosis factor- (TNF-) to the tumor necrosis factor receptor 1 (TNFR1) site and TNF--induced nuclear factor -light-chain-enhancer of activated B cells (NF-B) activation in cell at a half-maximal inhibitory concentration (IC50) value of 10 M. Along with this is a study showing the isoindolyl derivative to exhibit low toxicity toward human hepatocellular liver carcinoma (HepG2) cells and its possible mode of activity based on molecular modeling analysis.

Pentannulation of Heterocycles by Virtue of Precious Metal Catalysis

“…2016, 11,642 -659 www.chemasianj.org (Scheme 23). [37] The reactionc onditions proved to be general, and as malll ibrary was prepared in moderate to excellent yields (24 examples, 40-99 %y ield). Moreover,e nantioenriched products were obtained when this transformation was carried out on enantioenriched 63.T his domino reactions tartedw ith 1,2-acyloxy migration and was followed by Nazarov-typec yclization (path a, Scheme 24), or alternatively, putative intermediate 65 underwent direct cyclization with chirality transfer (path b).…”

“…A new class of compounds, that is, tricyclic norbornane‐fused pyrrolidine derivatives 64 , with proinflammatory cytokine antagonist activity, were obtained in the gold(I)‐catalyzed cycloisomerization of 63 followed by Diels–Alder reaction (Scheme ) . The reaction conditions proved to be general, and a small library was prepared in moderate to excellent yields (24 examples, 40–99 % yield).…”

Gold‐Catalyzed Double Cycloisomerization of 1‐Ene‐4,10‐diynyl Esters to Bicyclo[6.3.0]undeca‐2,4,9‐trienyl Esters

“…An illustrative example of this is the Au I ‐catalyzed Rautenstrauch rearrangement of 1,4‐enyne esters to cyclopentenones (Scheme , path a) ,. Following these seminal works, we disclosed that if an alkene group was suitably placed in the putative cyclopentenylgold complex I , a subsequent Diels–Alder reaction could be realized to afford isoindoles ( 3 ) . By replacing the alkene moiety with an alkyne tether, a Brønsted acid‐catalyzed formal [3+2] cycloaddition/deacetylation pathway to furnish bridged cyclic ketones ( 4 ) could also be accomplished .…”

Transition‐Metal‐Catalyzed Transformations of 1‐Alkenylpropargyl Alcohols and Esters: Valuable Cascade Reactions for Increasing Structural Complexity

“…The cyclopentadiene products 11 can be intercepted by alkenes in intramolecular Diels–Alder cyclizations, yielding annulated norbornene derivatives 12 with high diastereoselectivity (Scheme ). Gold(I)–NHC complexes were reported to catalyze this cascade transformation effectively …”