Kumada cross-coupling reactions

Name Reactions, 4th ed., DOI 10.1007/978-3-642-01053-8 144, Springer-Verlag Berlin Heidelberg 2009 

Sumitani, K. Kiso, Y. Zembayashi, M. Fujioka, A. Kodma, S.-i. Naka-jima, I. Minato, A. Kumada, M. Bull. Chem. Soc. Jpn. 1976,49,1958-1969. 

Meth-Cohn, O. Jiang, H. J. Chem. Soc., Perkin Trans. 1 1998, 3737—3746. 

Fuchter, M. J. Kumada cross-coupling reaction. In Name Reactions for Homologa-tions-Part I Li, J. J., Corey, E. J., Eds. Wiley Sons Hoboken, NJ, 2009, pp 47-69. (Review). 

4-Bis(4-methoxyphenyl)-l, 3-difliiadiphosphetane-2,4-disulfide transforms the carbonyl groups of aldehydes, ketones, amides, lactams, esters and lactones into the corresponding thiocarbonyl compounds. Cf. Knorr thiophene synthesis. 

Name Reactions A Collection of Detailed Mechanisms and Synthetic Applications, DOI 10.1007/978-3-319-03979-4 154, Springer International Publishing Switzerland 2014 

Example 6, Nickel-catalyzed Kumada leaction of tosylalkanes  

The Kumada cross-coupling reaction (also occasionally known as the Kharasch cross-coupling reaction) is a nickel- or palladium-catalyzed cross-coupling reaction of a Grignard reagent with an organic halide, triflate, etc. 

Indole synthesis using the palladium-catalyzed coupling reaction of an -iodoaniline with a propargyl alcohol. 

Nishikawa, T. Wada, K. Isobe, M. Biosci. Biotech. Biochem. 2002, 66, 2273. 

4-Bis-(4-methoxyphenyl)-[ 1,3,2,4]dithiadiphosphetane 2,4-disulfide, transforms the carbonyl groups of ketones, amides and esters into the corresponding thiocarbonyl compounds. 

While the nickel-catalyzed reaction facilitates oxidative addition of substrates problematic to palladium-mediated processes, there is still a great deal of interest in the palladium-catalyzed Kumada cross-coupling reaction due to its enhanced chemoselectivity. Also, as mentioned previously, one distinct advantage of the palladium-catalyzed procedure, is that it allows versatile organolithium reagents to be used as an alternative to Grignard 

Ikunaka et al. employed a Kumada cross-coupling reaction. Conversion of commercially available (i )-BINOL (47) to the bistriflate 48, followed by Kumada cross-coupling with methylmagnesium iodide, gave access to methyl derivative 49 in good yield. The synthesis proved reliable and scalable as apposed to other cited reports. 

For the above example however, the Kumada cross-coupling is not stereoselective and the source of chiral information lies in the commercially available, but relatively expensive (./ )-BINOL (47). An impressive alternative was reported 15 years previous to this by Hayashi and coworkers. Asymmetric cross-coupling of aryl Grignard 51 with napthyl bromide 52, gave the desired product 49 in an impressive 95% ee. While other ligands had proved less successful in mediating an analogous transformation, the use of ferrocenylphosphine (5)-(/ )-53 dramatically improved the selectivity.  

There are several examples of the synthesis of naturally isolated, complex molecular architectures utilizing the Kumada cross-coupling as a key step. For example, the enantioselective synthesis of (-i-)-ambruticin (59) was reported from the laboratories of Jacobsen. Conversion of an ( )-vinyl iodide 57 to diene 58 was achieved in good yield using a Kumada crosscoupling. The stereochemistry of the vinyl iodide 57 was conserved in the transformation. 

Cross-Coupling of Knochel-type Grignard Reagents and Triarylmagnesiates 

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Scheme 6.40 Negishi and Kumada cross-coupling reactions.

Walla, P., Kappe, C. O. Microwave-assisted Negishi and Kumada cross-coupling reactions of aryl chlorides. Chem. Common. 2004, 564-565. 

Air-stable and readily accessible /f-phosphonate PinP(0)H (231) facilitates highly efficient palladium-catalyzed Kumada cross-coupling reactions of electron-rich as well as electron-poor tosylates, including heteroaromatic electrophiles (Scheme 92). ... 

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