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Synthesis of 5,5,10,10‐tetramethyl‐1‐oxacyclotridecane‐6,7,8,9‐tetrone – on the mechanism of the Rubottom reaction
Author(s) -
Gleiter Rolf,
Staib Michael,
Ackermann Uwe
Publication year - 1995
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.1995199509230
Subject(s) - chemistry , diastereomer , enol , silylation , silyl enol ether , solvent , enol ether , diketone , reaction mechanism , silyl ether , medicinal chemistry , stereochemistry , organic chemistry , catalysis
Abstract The synthesis of 5,5,10,10‐tetramethyl‐1‐oxacyclotridecan‐6,7,8,9‐tetrone ( 12 ) was achieved via a multistep procedure involving an oxidation known as the Rubottom reaction. The key intermediates were the dialdehyde ( 25 ), the diacid ( 33 ), the cyclic diketone ( 39 ) and the bis(silyl enol ether) ( 42 ). The oxidation of 42 with m CPBA yielded two diastereomers, the syn and anti bis(α‐hydroxy ketones) ( 44, 45 ) the ratio of which depends strongly on the solvent used. This result combined with the isolation of the diepoxide ( 43 ) gives an insight into the stereochemistry of the Rubottom reaction.