Hiyama coupling reaction

Hiyama coupling reactions applying primary and secondary alkyl bromides or iodides 1 and aryltrifluorosilanes 21 (M = SiF3) catalyzed by 6.5 mol% NiBr2 DME and 7.5 mol% bathophenanthroline 12 are viable to obtain branched... 

Hinsberg Synthesis of Thiophene Derivatives Hiyama (see Nozaki-Hiyama Coupling Reaction) Hoch-Campbell Aziridine Synthesis Hoesch (see Houben-Hoesch Reaction)... 

Nozaki-Hiyama Coupling Reaction (Nozaki-Hiyama-Kishi Reaction)... 

Srimani D, Sawoo S, Sarkar A (2007) Convenient synthesis of palladium nanoparticles and catalysis of Hiyama coupling reaction in water. Oig Lett 9 3639-3642... 

Lee DH, Jung JY, Jin MJ (2010) General and highly active catalyst for mono and double Hiyama coupling reactions of unreactive aryl chlorides in water. Chem Commun 46 9046-9048... 

Alkyl bromides and iodides can participate in Hiyama coupling reactions when bulky alkyl phosphine ligands are employed (Scheme 2.111) The reaction can even works at room temperature. 

Diazotized dendrimers were rednced with Au(III) [297] or Pd(II) [298] to provide the corresponding Am( p) or Pd(np) core dendrimers. Palladinm-grafted dendrimer nanoparticles catalyze the redaction of C=C and C=C at room temperature. The Pd-core dendrimer was also found to be a good catalyst in Suzuki, Stille, and Hiyama coupling reactions [299] with a good recovery and recyclability in Suzuki coupling reactions. 

Triene Synthesis. Like other vinylsilanes, 1-trimethylsilyl-1,3-hutadiene can be used in a Hiyama coupling reaction with vinyl iodides (eq 8)7... 

In Scheme 10, HMG-CoA reductase inhibitor 92 was synthesized via a Suzuki coupling approach. Hiyama s group also carried out a Hiyama coupling to make the same compound (93TL8263). Vinylsilane 119 was prepared by platinum-catalyzed reaction from terminal alkyne 89. 

Hiyama, T. Organosilicon Compounds in Cross-Coupling Reactions. In Metal Catalyzed Cross-Coupling Reactions, Diederich, F., Stang, P. J., Eds. Wiley-VCH Weinhein, 1998 Chapter 10. 

In the context of NHC/metal catalysed cross-coupling reactions, the only example of a Hiyama reaction was reported by Nolan using an in situ protocol by mixing Pd(OAc)j and IPr HCl for the formation of the catalyst. Activated aryl bromides and chlorides, such as 2-chloropyridine, were coupled with phenyl and vinyl-trimethoxysilane in good yields [123] (Scheme 6.39). 

Hiyama, T. in Metal-Catalyzed Cross-Coupling Reactions 1998, Eds Diederich, F. Stang, P.J. Publisher Wiley-VCH Verlag GmbH, Weinheim, Germany, chapter 10, 421-53. 

Pitavastatin (3) was launched in 2003 and is currently marketed in Japan under the trade name Livalo . Like rosuvastatin and fluvastatin, pitavastatin is a completely synthetic HMG-CoA reductase inhibitor that was developed by Kowa, Nissan Chemical, and Sankyo (Sorbera et al., 1998). Multiple syntheses of pitavastatin have been reported and an exhaustive review of these efforts is beyond the scope of this text (Hiyama et al., 1995a, b Minami and Hiyama, 1992 Miyachi et al., 1993 Takahashi et al., 1993, 1995 Takano et al., 1993). Instead, we will focus our discussion on two related and innovative synthetic approaches that differ strategically from the routes we have previously examined for rosuvastatin and fluvastatin. These routes to pitavastatin employed palladium-mediated coupling reactions to install the 3,5-dihydroxyheptanoic acid side-chain. This key retrosynthetic disconnection is highlighted in Scheme 12.6, in which a suitable functionalized side-chain (52 or 53) is attached to the heterocyclic core of pitavastatin (51) through palladium-mediated coupling. 

Reaction with Organosilicon Reagents (Hiyama Coupling) 668... 

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