Issue in Honor of Prof. Eusebio Juaristi ARKIVOC 2005 (vi) 153-161
ISSN 1424-6376 Page 153
©
ARKAT USA, Inc
An efficient synthesis of functionalized α-amino-phosphine oxides
and -phosphonates by addition of aminoalcohols to
4-phosphorylated-1,2-diaza-1,3-butadienes
Francisco Palacios,* Domitila Aparicio, Jesús M. de los Santos, Roberto Ignacio,
and Yago López
Departamento de Química Orgánica I, Facultad de Farmacia, Universidad del País Vasco,
Apartado 450. 01080 Vitoria-Gasteiz, Spain
E-mail: qoppagaf@vf.ehu.es
Dedicated to Professor Eusebio Juaristi on the occasion of his 55
th
anniversary
(received 30 Mar 05; accepted 02 May 05; published on the web 04 May 05)
Abstract
Michael addition (1,4-addition) of achiral and chiral aminoalcohol derivatives to 1,2-diaza-1,3-
butadienes derived from phosphine oxides and phosphonates gives functionalized α-amino-
phosphine oxides and -phosphonates.
Keywords: 1,2-Diaza-1,3-butadienes, functionalized α-amino-phosphine oxides and -
phosphonates, Michael addition, phosphorylated hydrazones
Introduction
1,2-Diaza-1,3-butadienes I (Figure 1) are widely used intermediates in organic synthesis
1,2
because they offer easy access to a broad range of heterocycles. Many of these heterodienes
substituted on the terminal nitrogen (N-1) (I, R
1
= Me, Ar, ArSO
2
, COR, CO
2
R, CONR
2
)
1a,3
and
on the terminal carbon (C–4) (I, R
3
= Me, Br, Cl, COR, CO
2
R, CONR
2
, D-arabino-
(CHOAc)
3
CH
2
OAc)
1a,2b,3,4
have been described. However, very little information about the
behaviour of 1,2-diaza-1,3-butadienes II (Figure 1) containing phosphorus substituents at C–4
have been reported.
5
Furthermore, it is known that phosphorus substituents regulate important
biological functions,
6
and the introduction of organophosphorus functionalities in simple
synthons could be very interesting for the preparation of biologically active compounds.