Fujiwara-Moritani reaction asymmetric

Mikami and co-workers reported the first examples of an asymmetric Fujiwara-Moritani reaction," which is generally catalyzed by chiral Pd(II) complexes... 

By using an LX-type ligand, the catalytic asymmetric Fujiwara-Moritani reaction of benzene with cyclic olefins can afford the chiral phenyl-substituted cyclic olefins through syn p-H elimination from the opposite (y) side to the phenyl group (Scheme 32) [160]. 

Complexes 24, 25, and 26 aU possess two neutral and two anionic ligands, respectively, and they are included in this section although they do not have halide ligands. Each of C2-symmetric bisoxazoline complexes 24 and 25 has two tiifluoroacetate ligands and is a good catalyst for asymmetric Wacker-type cyclization. Complex 26, applied to the asymmetric Fujiwara-Moritani reaction, is a rare example of having anionic chelate... 

In 1999, Mikami and co-workers reported the first example of asymmetric Fujiwara-Moritani reaction catalyzed by Pd" and sulfonylamino-oxazoline ligand (Scheme 5.12a). A 1 1 complex between the chiral ligand and Pd(OAc)2 could be the active catalyst in this asymmetric Fujiwara-Moritani reaction. This method provides a convenient process to synthesize aromatic C—H bond activation/olefin coupling products but with moderate enantioselectivity. 

Scheme 5.12 Pd-catalyzed asymmetric Fujiwara-Moritani reaction reported by Mikami and Oestreich.

Scheme 5.39 The first asymmetric intramolecular Fujiwara-Moritani reaction reported by Mural.

Mikami, K., Hatano, M. and Terada, M. (1999) Catalytic C—H bond activation-asymmetric olefin coupling reaction the first example of asymmetric Fujiwara-Moritani reaction catalyzed by chiral paUadium(II) complexes. Chem. Lett., 28, 55-6. 

Scheme 7.45 Catalytic asymmetric intermolecular Fujiwara-Moritani reaction.

Asymmetric Oxidative Arene-Alkene Coupling (Fujiwara-Moritani) Reactions... 

The Fujiwara-Moritani reaction is a Pd-catalyzed oxidative coupling of an unfunctionalized arene with an alkene, in which a C-H bond of the arene is directly converted to a new C-C bond. Developing an asymmetric version of this type of reaction remains a formidable challenge in modern synthetic... 

In 1999, Mikami s group reported the first example of an intermolecular asymmetric Fujiwara-Moritani reaction of benzene with cyclic alkenes using a Pd catalyst co-ordinating to a chiral sulfonylamide-oxazoline ligand (Scheme 7.24). With PhCOs Bu as the oxidant, the coupling reaction occurred with moderate enantioselectivity (up to 49% ee), although the chemical yield was low. The reaction is considered to involve the formation of a phenyl-Pd species via electrophilic C-H substitution by Pd(ii), and Heck-type cyclization followed by re-oxidation of the resultant Pd(0) species. 

The catalytic asymmetric Fujiwara-Moritani-type allylation reaction of indoles and pyrroles was reported by Oestreich and co-workers. Moderate yields and ee were realized by using novel oxazoline ligands and a stereo-genic quaternary center was formed (Scheme 5.12b). Nevertheless, it still leaves room for improvement, probably by designing new ligands. 

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