オクタカルボニルジコバルトを用いる1-アルキニルおよび1-アレニルシクロプロパノールの転位反応
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概要
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A novel rearrangement of 1- (1-alkynyl) cyclopropanols to 2-cyclopenten-1-ones proceeded on complexation of their alkynyl part with Co<SUB>2</SUB> (CO) <SUB>8</SUB>. In the case of reactions of 1-alkynylcyclopropanols with an alkyl substituent on the cyclopropane ring, either 4-substituted or 5-substituted 2-cyclopenten-1-ones could be selectively obtained by appropriate choice of stereochemistry and protective group of the substrates. This rearrangement was successfully applied to the annulation of cyclopentenones onto cycloalkenes. Furthermore, the rearrangement was found to proceed catalytically on addition of triarylphosphite as a ligand.<BR>The same type of rearrangement proceeded when 1- [<I>o</I>- (1-alkynyl) phenyl] cyclopropanols were employed as substrate ; these being converted to 2, 3-dihydro-l-naphthalenone derivatives on heating their Co<SUB>2</SUB> (CO) <SUB>6</SUB> complexes in 2-propanol. Furthermore, a new type of isomerization-cyclization reaction proceeded to give 3a, 4-dihydro-3 H-cyclopenta [a] inden-2-one derivatives when the same reaction was carried out in the presence of DABCO.<BR>Finally a novel transformation of 1-allenylcyclopropanols into substituted 1, 4-hydroquinones was developed utilizing the interaction of 1, 2-propadienes and Co<SUB>2</SUB> (CO) <SUB>8</SUB>. This reaction was applied to the synthesis of vitamin E and K analogs.
- 社団法人 有機合成化学協会の論文
- 1998-12-01