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Zur Reaktion von Dialkylphosphiten mit α‐Enonen, II. 2:1‐Addukte aus Dimethylphosphit und α‐Enonen: Darstellung von (1‐Hydroxy‐1,3‐alkandiyl)diphosphonaten und 5‐Dimethoxyphosphoryl‐2‐methoxy‐1,2‐oxaphospholan‐P‐oxiden
Author(s) -
Öhler Elisabeth,
Zbiral Erich
Publication year - 1991
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.199119910140
Subject(s) - chemistry , diphosphonates , adduct , phosphonate , medicinal chemistry , moiety , yield (engineering) , stereochemistry , organic chemistry , genetics , materials science , bone resorption , metallurgy , biology
Reaction of Dialkyl Phosphites with α‐Enones, II. – 2:1 Adducts from Dimethyl Phosphite and α‐Enones: Synthesis of (1‐Hydroxy‐1,3‐alkanediyl)diphosphonates and 5‐Dimethoxyphosphoryl‐2‐methoxy‐1,2‐oxaphospholane P‐Oxides On NaOCH 3 ‐catalyzed reaction with two equivalents of dimethyl phosphite ( 2 ), various α‐enones 1 are transformed into the diphosphonates 5 (e.g. 5a, 5b, 5e, 5f ), which, depending on the structure of the enone, can further react with ring closure to give the 1,2‐oxaphospholanes 6 (e.g. 6c, 6g, 6h ), or with phosphonate‐phosphate rearrangement of the α‐hydroxyphosphonate moiety to yield compounds 7 (e.g. 7d ). The formation of the 2:1 adducts is believed to occur via addition of 2 to the carbonyl group of the (3‐oxoalkyl)phosphonates 4 , formed from thermodynamically controlled 1,4 addition of 2 to 1 . Compounds 4 could also be treated with 2 to yield 2:1 adducts (e.g. 4c → 5c, 4d → 5d, 4d → 7d ).