Lewis Acid Promoted Tandem Intermolecular Diels−Alder/Intramolecular Allylation Reactions of Silyl-Substituted 1,3-Butadienes Leading to Multisubstituted 7-Norbornenones and Related Polycyclic Compounds

Abstract

7-Norbornenones of exo,exo-disubstituted patterns were formed highly selectively in good yields from Lewis acid-promoted tandem intermolecular Diels-Alder/intramolecular allylation reactions. The intermolecular Diels-Alder reaction between 1,4-bis(trimethylsilyl)-1,3-butadienes or 1-trimethylsilyl-1,3-butadienes with maleic anhydride in the presence of newly sublimed AlCl3 afforded their corresponding cycloaddition adducts, which underwent AlCl3-mediated intramolecular allylation of the carbonyl group by the in situ generated allylsilane moiety affording 7-norbornenones of exo,exo-disubstituted patterns.

Aluminum‐Based Catalysts for Cycloaddition Reactions: Moving One Step Ahead in Sustainability

“…Newly sublimed AlCl 3 can catalyze cycloaddition of 1,4‐bis(trimethylsilyl)‐1,3‐butadienes or 1‐trimethylsilyl‐1,3‐butadienes with maleic anhydride to form 7‐Norbornenones of exo or exo‐disubstituted patterns. Diels‐Alder reaction between these two moieties afforded their corresponding cycloaddition adducts, which underwent AlCl 3 ‐mediated intramolecular allylation of the carbonyl group by the in situ formed allylsilane moiety delivering 7‐norbornenones of exo , exo ‐disubstituted patterns . The Diels‐Alder reaction along with intramolecular allylation forms an efficient route for the development of multi‐substituted 7‐norborneones.…”

Regioselective Allylation of Carbon Electrophiles with Alkenyl­silanes under Dual Catalysis by Cationic Platinum(II) Species

“…Further effort was made to expand the scope of the carbon electrophile; the allylation of carboxylic anhydrides was examined (Scheme 4 and Table 10). 29 The platinum(II)catalyzed reaction of acetic anhydride (8a) with alkenylsilane 2a by a one-step method (method A) gave β,γ-unsaturated ketone 9a in good yield (entry 1); contamination with a trace amount of α,β-unsaturated ketone 9a′ was detected by 1 H NMR analysis. The reaction of 8a was carried out also by a stepwise method (method B), in which 2a alone was initially subjected to platinum(II) catalysis, and then 8a was added to the resultant mixture.…”

Zirconacycle-mediated synthesis of carbocycles

“…A number of methods have been developed for constructing cyclohexene derivatives [86][87][88][89][90][91][92]. Among them, the most notable reaction is the Diels-Alder reaction using dienes and alkenes.…”