Cross with allylic alcohol derivative

Palladium-catalyzed cross-coupling of 19 with allyl bromide occurs exclusively at the vinylstannane moiety to give 1-ethoxy-1-silyl-1,4-diene 20. The following ether exchange with allyl alcohol causes the Glaisen rearrangement to give an acylsilane derivative 21 (Scheme 64).2... 

Finally, benzenepolycarboxylates were obtained by ruthenium-catalyzed cross-benzannulation of acetylenedicarboxylates with allylic compounds [52] (Eq. 39). A ruthenacyclopentene is postulated to occur via oxidative coupling of one molecule of alkyne with allylic alcohol. Subsequent insertion of another molecule of alkyne gives the corresponding polysubstituted benzene derivatives. 

As discussed in Section 1.2.4, the Pd- or Ni-catalyzed cross-coupling involving allyl, benzyl, and propargyl electrophiles takes place with a wide variety of leaving groups. Indeed, virtually all types of allylic alcohol derivatives, including phosphates, carbonates, carboxylates, ethers, and silyl ethers, can be employed. 

Negishi and his co-workers have developed several approaches to allylated arenes involving cross-coupling reactions. Preliminary studies established that aryl-aluminium, zirconium, or zinc compounds readily undergo palladium-catalysed cross-coupling with allylic halides or acetates (Scheme 19). Later in the year it was shown that allylic alcohol derivatives containing OAlR2,... 

Aiming at easier workup conditions, immobilization of several transition metal catalysts, which show activity for the epoxidation of allylic alcohols, on polymer support has been investigated. For example, Suzuki and coworkers incorporated an oxo-vanadium ion into cross-linked polystyrene resins functionalized with iminodiacetic acid or diethylenetri-amine derivatives (Scheme 57), which afforded a heterogeneous catalyst that can promote... 

Alkenyl-aluminium or -zinc species cross-couple with allylic halides or derivatives of allylic alcohols (c.g. acetates or phosphates) under the influence of Pd(PPh3)4 to give 1,4-dienes. In favourable examples coupling occurs with complete retention of stereo- and regio-chemistry of both alkenyl and allyl substrates, and it is free from formation of homocoupled products (Scheme 73). However, partial allylic inversion was observed in reactions involving E-crotyl... 

The palladium-mediated cross-coupling of organozinc reagents, derived from the asymmetric carboalumination of allyl alcohol, with (iodoethynyl)trimethylsilane (eq 9), has also been reported en route to callystatin... 

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