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note
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3e (1 atm) at 80 °C in toluene afforded 2a in 91% yield; however, under identical conditions, a complex mixture was formed in the reaction of 1k. For additional catalysts examined, see Supporting Information.
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note
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Other solvents produced lower yields of cyclized products: toluene, 22%; THF, 0%; acetonitrile, 21%; nitromethane, 6%.
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Enantioenriched ethers were prepared from the corresponding alcohols prepared according to 1k and 1l: (a) Frantz, D. E.; Fässler, R.; Carreira, E. M. J. Am. Chem. Soc. 2000, 122, 1806.
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33748800691
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note
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The absolute configuration of 21 was assigned using the mandelate ester method on alcohol 15 (see Supporting Information).
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Reaction of enantioenriched ether 1c (89% ee) gave nearly racemic indenyl ether 2c (9% ee). Similarly, almost racemic 2c was observed at 50% conversion, while 1c was recovered without substantial racemization.
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A mechanism involving anti-addition of an alkyne nucleophile to an allyl or arene-gold(1) complex (as proposed for Pd in ref 7b) would also account for the observed overall inversion. However, this mechanism is not consistent with the observation that, under identical conditions, styrene 16 was recovered unreacted.
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