Organostannanes cross-coupling

The late Professor J. K. Stille pioneered the development of a very effective and versatile palladium-mediated C-C bond forming method - the palladium-catalyzed cross-coupling of organic electrophiles with organostannanes.48 This process continues to enjoy much success in organic synthesis because it proceeds in high yields under mild reaction conditions and because it tolerates a... 

Since its introduction by Allred and Liebsekind in 1996 [114], copper thiophene-2-carboxylate (CuTC) has emerged as a mild and useful reagent for mediating the cross-coupling of organostannanes with vinyl iodides at room temperature. CuTC is especially effective for substrates that are not stable at high temperature. In Paterson s total synthesis of elaiolide, he enlisted a CuTC-promoted Stille cyclodimerization of vinyl iodide 131 to afford the 16-membered macrocycle 132 under very mild conditions [115]. 

Palladium-catalyzed cross-coupling reaction of organostannanes with organic halides, triflates, etc. For the catalytic cycle, see Kumada coupling on page 345. 

Palladium- and copper-catalysed cross-coupling of organotellurium dichlorides with organostannanes and organoboronic acids... 

Scheme 17 Cross-coupling reaction of Ar3BiX2 with organostannanes...

Carbonylative cross-coupling reaction between triarylbismuth(V) compounds and organostannanes is smoothly catalyzed by PdCl2 under 1 atm CO at room temperature (Scheme 48) [34]. Not only arylstannanes, but also heteroaryl-, alkynyl-, and vinyltributylstannanes were employed efficiently. 

T. Forngren, Y. Andersson, B. Lamm, B. Langstrom, Synthesis of [4-F-18]-1-bromo-4-fluorobenzene and its use in palladium-promoted cross-coupling reactions with organostannanes, Acta Chem. Scand. 52 (1998) 475-479. 

Synthesis of a-fluoro-a,/3-unsaturated ketones via palladium-catalyzed cross-coupling reaction of 1-fluorovinyl halides (79) with organostannanes (80)... 

C. Chen, K. Wilcoxen, C.Q. Fluang, N. Strack, J.R. McCarthy, New methods for the synthesis of fluoro olefins via the palladium catalyzed cross-coupling reaction of 1-fluorovinyl halides with organoboranes and organostannanes, J. Fluor. Chem. 101 (2000) 285-290. 

In 2001, Nolan described the palladium/imidazoilium salt-catalyzed coupling of aryl halides with hypervalent organostannanes.The imidazolium salt 36 in combination with Pd(OAc)2 and TBAF was found to be most effective for the cross-coupling of aryl bromides and electron-deficient aryl chlorides with aryl and vinyl stannanes. 

Sphinx Pharmaceuticals101 patented successful Stille (with a resin-bound organostannane) and Suzuki (with a supported boronic acid) cross-couplings. In the same patent, they also reported a coupling of a phenylacety-lene with a resin-bound bromide wherein Pd(OAc)2 was the catalyst (Scheme 50). 

It was also discovered that aryl and vinyl iodides, bromides, and triflates participated efficiently in cross-coupling reactions with organostannanes when catalyzed by palladlum-on-carbon in the presence of Cu(l) as cocatalyst.1... 

Cross-coupling reactions of iodonium salts with terminal alkynes or organostannanes can also be effectively catalyzed by Cul, MnCl2 4H20, or Ni(acac)2 [56,58,103,104]. 

Saa, J. M. Martorell, G. Garda-Raso, A. Palladium-catalyzed cross-coupling reactions of highly hindered, electron-rich phenol triflates and organostannanes./. Org. Chem. 1992, 57, 678-685. 

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