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Use of a steric demanding nucleophile increased the selectivity of alkylation at the unsubstituted allylic terminus; see ref 14e.
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Akermark reported that 2,9-disubstituted-1,10-phenanthroline could stabilize anti π-allyl palladium complex and its use for Pd-catalyzed allylic alkylation. The reaction of (Z)-2-hexenyl acetate with diethyl sodiomethylmalonate gave (Z)-product in 72% selectivity; see ref 14a.
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A complex of terminal alkenes is more stable than that of internal alkenes: see ref 20b.
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3)], To avoid a steric repulsion of the substituted allylic terminus, triphenyl phosphite coordinates trans to the substituted allylic terminus.
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9-catalyzed reaction of (E)-crotyl acetate with dimethyl sodiomalonate gave the product from the alkylation at the substituted allylic terminus as a major product, whereas the same reaction of (Z)-crotyl acetate gave the product from the alkylation at the unsubstituted allylic terminus as a major product; see ref 11 d.
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