ISSN:
0009-2940
Keywords:
α-Enones, regioselective 1,2-addition of dimethyl phosphite to
;
Allylic rearrangement of dialkyl (1-hydroxy-2-alkenyl)phosphonates
;
1-Alkenylphosphonates, 3-acetyloxy-
;
1-Alkenylphosphonates, 3-hydroxy-
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Reaction of Dialkyl Phosphites with α-Enones, I. - Synthesis and Allylic Rearrangement of Dimethyl (1-Hydroxy-2-alkenyl)- and (1-Hydroxy-2-cycloalkenyl)phosphonatesVarious β,γ-unsaturated α-hydroxyphosphonates 3 are prepared in good yields by NaOCH3-catalyzed regioselective 1,2-addition of dimethyl phosphite to acyclic and cyclic α-enones at -35°C. On acid-catalyzed acetylation, the allylic α-hydroxyphosphonates 3 (R1, R2 + H) rearrange under thermodynamic control; yielding the new 3-acetyloxy-1-(cyclo)alkenyl derivatives 8, from which the transposed allylic alcohols 11 are readily obtained. Using shorter reaction times, acetylation of compounds 3 affords mixtures of 1- and 3-acetylated products, 10 and 8, respectively.
Additional Material:
4 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240126
