Venkat Reddy Chintareddy - P[N(i-Bu)CH2CH2]3N: Nonionic Lewis Base for Promoting the Room-Temperature Synthesis of α,β-Unsaturated Esters, Fluorides, Ketones, and Nitriles Using Wadsworth−Emmons Phosphonates

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      Publication Details (including relevant citation   information):

      J. Org. Chem., 2010, 75 (21), pp 7166–7174

     

      Abstract:

      The bicyclic triaminophosphine   P(RNCH2CH2)3N (R =   i-Bu, 1c) serves as an effective   promoter for the room-temperature stereoselective synthesis of   α,β-unsaturated esters, fluorides, and nitriles from a wide array   of aromatic, aliphatic, heterocyclic, and cyclic aldehydes and   ketones, using a range of Wadsworth−Emmons (WE) phosphonates.   Among the analogues of 1c [R = Me   (1a), i-Pr (1b), Bn   (1d)], 1a and   1b performed well, although longer reaction   times were involved, and 1d led to poorer yields   than 1c. Functionalities such as cyano, chloro,   bromo, methoxy, amino, ester, and nitro were well tolerated. We   were able to isolate and characterize (by X-ray means; see above)   the reactive WE intermediate species formed from   2b and 1c.

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