85656-30-0Relevant academic research and scientific papers
Photoinduced molecular transformations. 157. A new stereo- and regioselective synthesis of 2,6-diaryl-3,7-dioxabicyclo[3.3.0]octane lignans involving a β-scission of alkoxyl radicals as the key step. New total syntheses of (±)-sesamin, (±)-eudesmin, and (±)-yangambin
Suginome,Orito,Yorita,Ishikawa,Shimoyama,Sasaki
, p. 3052 - 3064 (1995)
New total syntheses of naturally occurring 2,6-diaryl-3,7-dioxabicyclo[3.3.0]octane lignans, (±)-sesamin and (±)-eudesmin, and the first total synthesis of (±)-yangambin were achieved according to a general method devised by Suginome and colleagues for replacing the carbonyl group of the cyclopentanone ring with an oxygen atom to give a corresponding tetrahydrofuran ring involving a regioselective β-scission of alkoxyl radicals; arylation of dimethyl, diallyl, or dibenzyl 3,7-dioxobicyclo[3.3.0]octane-2,6-dicarbonate (18 and 19a,b) with aryllead triacetate 9a-c, followed by dealkoxycarbonylation of the resulting arylated product 20a-f, gave 2,6-diaryl-3,7-dioxobicyclo[3.3.0]octane 21a-c. A regioselective Baeyer-Villiger oxidation of 21a-c with m-CPBA-NaHCO3 or -K2CO3 gave the corresponding δ-lactone 22a-c, which was reduced with DIBAL to give the corresponding lactol 23a-c. The irradiation of a solution of the hypoiodite of 23a-c, generated in situ with mercury(II) oxide-iodine, in benzene with Pyrex-filtered light resulted in a regioselective β-scission of the corresponding alkoxyl radical to give iodo formate 24a-c. Heating 24a-c in MeOH with NaBH4 gave (±)-sesamin (25a), (±)-eudesmin (25b), or (±)-yangambin (25c).
Arylation with Aryllead Triacetates Produced in situ by Mercury-Lead Exchange
Kozyrod, Robert P.,Pinhey, John T.
, p. 1155 - 1161 (2007/10/02)
The addition of lead tetraacetate to diphenylmercury in chloroform leads to the rapid formation of a solution of phenyllead triacetate, which has been used directly for the C-phenylation of ethyl 2-oxocyclopentanecarboxylate (1) and 2-nitropropane in good
ARYLATION WITH ARYLLEAD TRIACETATES PRODUCED IN SITU BY MERCURY-LEAD EXCHANGE
Kozyrod, Robert P.,Pinhey, John T.
, p. 5365 - 5366 (2007/10/02)
Reaction of a diarylmercury with lead tetraacetate to give an aryllead triacetate has been found to be a rapid reaction.The in situ generation of aryllead triacetates is thus an attractive alternative to the use of the purified reagents in the various electrophilic arylation reactions of these compounds.
