Use of polymer-supported phenyltin for the creation of aryl–aryl or aryl–heteroaryl bonds via Stille cross-coupling reactions

Synthesis, characterization and primary evaluation of the synthetic efficiency of supported vinyltins and allyltins

“…The experimental conditions used in solution for the vinyltributyltin derivatives can in general be extrapolated to supported analogues, resulting in similar yields, but with the advantage of minimizing pollution of final products by tin residues [9][10][11]. With supported crotyltins we have already observed a slower 1,3-metallotropy when compared to crotyltributyltin [25], and in the case of a-substituted c-ethoxyallyltins, their poor ability to give a 1,3-metallotropy due to the stabilization occurring in the Z-isomer, possibly because of coordination expansion of the tin atom by an oxygen one, results in a regioselective reaction affording the mono-protected a-glycols.…”

“…Pioneering studies have been devoted to supported organotin hydrides in reduction reactions [5] and to supported organotin oxides used as transesterification catalysts [6,7]. More recently, we have pointed out the efficiency of supported N-stannylanilines to obtain regioselective para-iodination [8] and, even more interestingly, we have used supported allyltins in order to obtain cleanly homoallyllic alcohols [9] or supported vinyltins and aryltins to achieve Stille-Migita cross-coupling reactions [10,11], a topic which remains of high interest as illustrated by reports from other groups [12][13][14]. High Resolution Magic Angle Spinning NMR (HRMAS NMR) [6] enables one to monitor more efficiently supported organotin reagents in order to exploit further their synthetic potential in novel solid phase synthetic procedures.…”

“…The obtained supported triorganotin halides 3a-c can be subsequently converted into supported triorganotin hydride 4 upon reaction with LiAlH 4 [10] or reacted with Grignard reagents or zinc reagents [9], affording a series of grafted allyltins, vinyltins and aryltins [9][10][11]. …”

Polymers for Green C–C Couplings

“…[114,115] They also used the polymersupported phenyl stannane 22 (Scheme 13) to synthesize biaryls by the Stille coupling with aryl halides. [116] In this case the polymer was reused, although an important decrease in the yield of the coupling product was observed upon recycling. Treatment of the used polymer with 2,4,6-trimercaptos-triazine before the next cycle is beneficial and allows a Polymers 24 bearing a Sn-alkynyl moiety have also been used in the recently developed tandem double Stille coupling of allyl halides and polymeric alkynyl stannanes to give trienynes (Scheme 17).…”

Selective Green Coupling of Alkynyltins and Allylic Halides to Trienynes via a Tandem Double Stille Reaction

“…[2] Its main drawback is the generation of toxic tin by-products, but there are some recent alternatives to overcome or alleviate this problem using polymeric recyclable tin reagents. [3,4] Although Stille couplings are well understood, certain combinations of reagents still give unexpected results. We report here the Pd-catalyzed reaction of alkynyltin compounds and allylic chlorides, a coupling that deviates from routine and results in the formation of trienynes, formally dimers of the expected 1:1 cross-coupling product.…”