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46.5.3.3 Method 3: Cyclization of Allenynes

DOI: 10.1055/sos-SD-046-00090

Gandon, V.; Thorimbert, S.; Malacria, M.Science of Synthesis, (200946218.

Chiral allenes are versatile intermediates for asymmetric syntheses via axial-to-centered chirality transfer.[‌146‌] Their use in the preparation of 1,3-dienes and especially exocyclic cycloalkenes has been reported; thus, treatment of a 1,2-dien-6-ynes with a slight excess of titanium(IV) isopropoxide and isopropylmagnesium chloride affords titanabicyclopentenes that can be reacted further with various aldehydes or imines to furnish functionalized E,E-exocyclic dienes. One such conversion, using the chiral allene 157 as the starting material, gives the diene 158 with complete conservation of stereochemistry (Scheme 55).[‌147‌]

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