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Scientific article
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Applications of the ß-Azidonation Reaction to Organic Synthesis. α,ß-Enones, Conjugate Addition, and γ-Lactam Annulation

Published inJournal of the American Chemical Society, vol. 120, no. 48, p. 12486-12499
Publication date1998
Abstract

The ß-azido functionalization reaction provides a mechanistically different enone synthesis that involves treatment of 2 with fluoride anion to effect desilylation and concomitant ß-elimination to give 3. Table 1 lists a number of examples of the direct conversion of a TIPS enol ether into the corresponding a,ß-enone via a ß-azido TIPS enol ether. The ß-azido group can be ionized with Me3Al or Me2AlCl and the intermediate enonium ion trapped by a variety of nucleophiles such as an allylstannane, electron-rich aromatics, TMS enol ethers, Et2AlCN, Me2AlCCR, Me4AlLi, and vinylaluminum reagents to give the products listed in Table 2. The diastereoselectivity of the reaction of a 4-substituted enonium ion with indole shows an unusual increase of selectivity with increasing temperature. Reduction of the azide 2 provides access to ß-amino TIPS enol ethers 5, which, for example, can be converted into a cinnamide derivative and cyclized via a putative “ene” process into a ?-lactam.

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Citation (ISO format)
MAGNUS, Philip et al. Applications of the ß-Azidonation Reaction to Organic Synthesis. α,ß-Enones, Conjugate Addition, and γ-Lactam Annulation. In: Journal of the American Chemical Society, 1998, vol. 120, n° 48, p. 12486–12499. doi: 10.1021/ja9829564
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