Intramolecular Cyclization of Tethered Phenyl Ketones. Complementary Stereochemical Results Arising from the Indium-Promoted Ring Closure of Allyl Bromides and the Fluoride Ion-Induced Desilylation of Allylsilanes
journal contributionposted on 06.11.1998, 00:00 by Leo A. Paquette, José L. Mendez-Andino
The intramolecular indium-promoted cyclization of 4‘-substituted (Z)- and (E)-7-bromo-5-heptenophenones has been examined in aqueous tetrahydrofuran. In every instance, ring closure occurred to deliver the syn-2-vinylcyclopentanol exclusively. The corresponding allylsilanes have been prepared as well, and the course of their fluoride ion-induced cyclization was also studied. In these systems, a kinetic bias for formation of the anti-2-vinylcyclopentanol is observed, although not with the same exclusivity. Accordingly, complementarity in product diastereoselectivity can be realized in purposeful fashion. The data acquired in this investigation suggest that the indium-catalyzed reactions involve intramolecularly coordinated transition states where development of a cis 5/6-bicyclic framework is most energetically feasible. In contrast, the silanes appear to utilize open-chain antiperiplanar transition states. While the latter are not particularly sensitive to double-bond geometry, they are responsive to steric compression involving the aryl group.
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DesilylationexclusivityComplementary Stereochemical Results ArisingantiperiplanarframeworkAllyl Bromidesvinylcyclopentanolfluorideallylsilaneintramolecularlyintramolecularcomplementaritysteric compressionring closureinvestigationcontrastformationciTethered Phenyl Ketonesbicyclicaryl groupFluorideClosuretetrahydrofurantransition statesIntramolecular CyclizationsilaneAllylsilanefashionbiaslattercyclizationinstancesynproduct diastereoselectivitybromodata