Polyene propargylic alcohols

Related tricyclic systems of guaiane sesquiterpenoids resanbUng the structure of globulol and epiglobulol have also been reported by Echavarren [77,78]. In his report, polyene propargylic alcohols are utilized to produce guaiane cores under gold catalysis (Scheme 7.55). 

SCHEME 7.55 Cycloisomerization of polyene propargylic alcohols under gold catalysis. 

Allylic metals, in propargylic alcohol alkylation, 11, 129 ir-Allylic palladium complexes, and carbocyclization, 11, 426 Allylic position, alkenes, dienes, polyenes, metallation, 9, 6 Allylic selenides, [2,3]sigmatropic rearrangement, 9, 481 Allylic substitution reactions for C-N bonds via amination... 

Optically active aliphatic propargylic alcohols are converted to corticoids (90% ee) via biomimetic polyene cyclization, and to 5-octyl-2(5ii)-furanone. The ee s of propargylic alcohols obtained by this method are comparable with those of the enantioselective reduction of alkynyl ketones with metal hydrides, catalytic enantioselective alkylation of alkynyl aldehydes with dialkyIzincs using a chiral catalyst ((S)-Diphenyl(l-methylpyrrolidin-2-yl)methanol) (DPMPM), and the enantioselective alkynylation of aldehydes with alkynylzinc reagents using A(A-dialkylnorephedrines. °... 

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