Module 10 : Phosphorus-Containing Compounds

Lecture 23 : Phosphorus-Containing Compounds

10.1.7 Mitsunobu Reaction

The alkoxyphosphonium ion generated from diethyl azodicarboxyliate (DEAD), triphenyl phosphine and alcohol undergoes reaction with nucleophile (usually carboxylic acid) by SN2 character (Scheme 13-14). The reaction exploits, first, the reactivity of the azo compound as an electrophile in the formation of the first phosphonium ion and, second, the good leaving group property of the reduced azo compound.

Scheme 13

Mechanism

Scheme 14

Examples

 

10.1.8 Vilsmeier-Haack Reaction

This reaction allows formylation of the reaction of activated alkenes as well as arenes (Scheme 15).

Scheme 15

Mechanism

The formylating agent is generated in situ from DMF and POCl 3 (Scheme 16).

Scheme 16