The Heck reaction is a powerful tool in the formation of carbon-carbon bonds. Cyclic olefins often produce a mixture of regioisomers due to isomerization of the newly formed double bond. Selectively controlling the extent of isomerization to give a single regioisomer would drastically improve the synthetic utility of such coupling reactions. Trineopentylphosphine (TNpP) and tert-?butyldineopentylphosphine (TBDNpP) have been shown to exhibit unique reactivity trends relative to tri-tert-butylphosphine (TTBP) due to their increased conformational flexibility. The innate selectivity of TNpP and TBDNpP to give different regioisomeric products in the Heck reaction of cyclic olefins will be discussed. The intramolecular trapping of migratory palladium in the Heck reaction of 2,3-dihydrofuran with 2-bromophenols or 2-bromoanilines to form epoxybenzoxepins and epoxybenzazepins, similar to those found in the core of the natural products of the spiroxin family and atkamine, will also be presented. Figure 1. <img src='https://acs-archive-assets2.s3.amazonaws.com/241nm/uploads/61925_bs.jpg' alt='' />

Utilizing neopentylphosphine ligands to control regioselectivity in the palladium-catalyzed Heck reaction of cyclic olefins

248th National Meeting (2014)

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