The use of TADDOL-based monophosphoramide has been demonstrated instead of BINAP in the reaction of intramolecular cyclization of cyclohexadienone derivatives (Scheme 11). This reaction can be performed in the absence of silver salt.

Scheme 11

Intermolecular Heck reaction is also well studied. For example, dihydrofuran reacts with phenyl triflate to give 2-phenyl-2,3-dihydrofuran along with small amount 2-phenyl-2,5-dihydrofuran in the presence of Pd-BINAP with excellent enantioselectivity (Scheme 12). A mechanism has been proposed to explain the high enantioselectivity of the major product and inversion configuration of the minor product (Scheme 13). It involves a kinetic resolution process that enhances the enantioselectivity of the major product.

Scheme 12

Scheme 13