Synthesis of 4,5,9,10-tetradehydroadamantan-2-one

Abstract

The first synthesis of the strained dicyclopropyl ketone, 4,5,9,10-tetradehydroadamantan-2-one, is described. This compound has been prepared in 10 steps from norbornadiene.If only nonbridgehead positions are connected by u bonds, then the carban skeleton of adamantanone (1) algo 1

Recent Advances in Synthesis of Cyclopropanes

“…The reaction works best with nitro compounds (pK a < 17) and is not applicable to the sulfonylderivatives (pK a ∼ 25). (16) Stereodivergent synthesis of almost enantiomerically pure and stereospecifically deuterium-labeled 2,2-dimethylcyclopropanols has been achieved by treating 2,2-dimethylpropane-1,3-diol dicarbamate with alkyllithium in the presence of (−)-sparteine (equation 17) 29 . (17) Stereochemical investigation on the vinylogous 1,5-elimination reactions of 16 to give cyclopropylalkenes has revealed high syn stereoselectively of the intramolecular S N process (equation 18) 30 .…”

Tetrakis(acetonitrile)copper(I) Perchlorate

“…2, 3 With acyclic cyclopropyl ketones, C-O epoxide bond cleavage occurs selectively, leading to a cyclopropylcarbinyl carbocation intermediate and subsequent thiomethyl group migration. The reagent can react with the adducts formed from acyclic or cyclic cyclopropyl ketones and tris(methylthio)methyllithium (see Tris(methylthio)methane); the products have been rationalized via the intervention of epoxide intermediates.…”

“…(2) C(SMe) 3 27:72 Cyclopropanations. Cu(MeCN) 4 ClO 4 can catalyze the cyclopropanation of tetramethylethylene (TME) with Ethyl Diazoacetate (EDA).…”

Synthesis of 4-Acetylisocoumarin: First Total Syntheses of AGI-7 and Sescandelin

“…Unfortunately, the separation of the desired product ( 5 and 16 ) from the unwanted minor isomer ( 17 and 15 ) was not an easy task. To circumvent this problem, the crude mixture of 5 and 17 was treated with Jones reagent to oxidize the aldehyde functional group of minor 15 to the carboxylic acid . This treatment enabled the efficient purification of AGI-7 ( 5 ) and did not affect the final isolated yield (56%) considerably.…”