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8 (<5% ee) and BINAP-platinum(II) (18% ee) complexes promoted the reaction: however, the enantioselectivity was poor.
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note
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6b required prolonged reaction times (7 days) and gave racemic products.
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In accord with a mechanism involving Irans addition to the alkyne, cyclization of a deutero-acetylene resulted in isolation of the adduct in which deuterium was only incorporated cis to the ketoester; however, this experiment was complicated by deuterium exchange of acetylenic proton.
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A mechanism involving alkyne activation by Pd(II) was excluded in isomerization of 1,6-enynes catalyzed by related cationic bis(phosphine)- palladium(II) complexes: Mikami, K.; Hatano, M. Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5767.
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2a
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