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Novel chiral 1-phosphono-1,3-butadiene for asymmetric hetero Diels–Alder cycloadditions with nitroso and azodicarboxylate dienophiles

✍ Scribed by Jean-Christophe Monbaliu; Bernard Tinant; Daniel Peeters; Jacqueline Marchand-Brynaert

Publisher
Elsevier Science
Year
2010
Tongue
French
Weight
227 KB
Volume
51
Category
Article
ISSN
0040-4039

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✦ Synopsis

Chiral 1-phosphonodienes bearing a bicyclic (R,R)-1,3,2-dioxaphospholane or a (R,R)-1,3,2-diazaphospholidine auxiliary are potent dienes for asymmetric hetero Diels-Alder reactions. Their reactivity towards model nitroso and azodicarboxylate dienophiles has been studied by means of theoretical chemistry at the B3LYP/6-31G** level. This model, taking solvent effects into account, allowed us to identify parameters governing the stereoselectivity of this reaction. Our study emphasizes a synergy effect when increasing the steric hindrance of substituents of both partners. This led us to predict high levels of diastereoselectivity for one diene. Accordingly, we have hereby illustrated a convenient and original synthesis of this diene and its cycloadditions with commercially available nitroso and azodicarboxylate dienophiles.

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