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Darstellung von (3‐Amino‐1‐alkenyl)phosphonsäuren aus allylischen α‐ und γ‐Hydroxyphosphonaten. Sigmatrope Umlagerung von (1‐Azido‐2‐alkenyl)phosphonsäureestern
Author(s) -
Öhler Elisabeth,
Kotzinger Silvia
Publication year - 1993
Publication title -
liebigs annalen der chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0170-2041
DOI - 10.1002/jlac.199319930147
Subject(s) - chemistry , allylic rearrangement , medicinal chemistry , stereochemistry , sigmatropic reaction , organic chemistry , catalysis
Synthesis of (3‐Amino‐1‐alkenyl)phosphonic Acids from Allylic α‐ and γ‐Hydroxyphosphonates. – Sigmatropic Rearrangement of Dialkyl (1‐Azido‐2‐alkenyl)phosphonates (3‐Azido‐1‐alkenyl)phosphonates 8 with R 1 = H are prepared regioselectively by reaction of secondary (1‐hydroxy‐2‐alkenyl)phosphonates 3 with TPP/DEAD/HN 3 and subsequent thermal 1,3‐rearrangement of the allylic α‐azidophosphonates 5 primarily formed. (3‐Azido‐1‐alkenyl)phosphonates 8 with R 1 ≠ H are conveniently obtained from the regioisomeric tertiary 3‐hydroxy derivatives 4 , which can be prepared either by allylic rearrangement of the corresponding α‐hydroxyphosphonates 3 , or by NaBH 4 reduction of the (3‐oxo‐1‐alkenyl) derivatives 7 . The synthetic utility of the azido compounds 8 is demonstrated by their conversion into the (3‐amino‐1‐alkenyl)phosphonic acids 11 and the N,O‐protected derivatives 12 and 13 , and to the saturated γ‐aminophosphonates 14 .