Phenyl tributylstannyl

Phenyl tributylstannyl tellurium decomposed during vacuum distillation and chromatography1. 

Pd(PPh3)4-Catalyzed Coupling of Phenyl Tributylstannyl Selenide with Aryl Iodides and Carbon Monoxide... 

Pd(PPh3)4 catalyzes the three-component coupling of phenyl tributylstannyl selenide 73 with aryl iodides and carbon monoxide to afford the corresponding selenol esters (Eq. 46) [96]. 

When phenyl tributylstannyl selenide 73 (see Fig. 7) was allowed to react with iodobenzene in the presence of a catalytic amount of Pd(PPh3)4 in toluene solution under carbon monoxide (5 atm) at 80 °C for 5 h, selenol ester was formed with 89% yield. Chloro- and bromobenzenes did not give the selenol ester under the same reaction conditions, but aryl iodides with various substituents on... 

Aryl and alkenyl phenyl sulfides are prepared by the reaction of aryl and alkenyl halides and inflates with tributylstannyl phenyl sulfide. 2-Chloropyrimidine (737) is used for the coupling[606,607]. The diaryl or divinyl sulfide 739 is prepared by the reaction of distannyl sulfide (738)[548], N,N-Diethylaminotributyltin (740) reacts with aryl halides to give arylamines[608]. 

Tributylstannyl)-3-cyclobutene-1,2-diones and 4-methyl-3-(tributylstan-nyl)-3-cyclobutene-l,2-dione 2-ethylene acetals undergo the palladium/copper-catalyzed cross coupling with acyl halides, and palladium-catalyzed carbon-ylative cross coupling with aryl/heteroaryl iodides [45]. The coupling reaction of alkenyl (phenyl )iodonium triflates is also performed by a palladium/copper catalyst [46],... 

The Stille adduct of 2-bromothiophene and l-ethoxy-2-tributyl-n-stannylethene or 1-ethoxy-l-tri-n-butylstannylethene is a masked thienyl aldehyde or a masked ketone, respectively [77-80]. Vinylstannane 93, derived exclusively as the -isomer from hydrostannation of bis(trimethyl-silyl)propargyl amine (92), was coupled with 2-bromothiophene to form ( )-cinnamyl amine 94 upon acidic hydrolysis [81, 82], In another case, stereoisomerically pure phenyl ( )-2-tributylstannyl-2-alkenoate 95, arising from Pd-mediated hydrostannation of phenyl ( )-2-alkynoate, was joined with 2-iodothiophene to deliver the stereodefmed trisubstituted a,p-unsaturated ester 96 [83, 84],... 

The arylation of the 1-tributylstannyl glycal 717 offers a synthetic route to chaetiacandin[585,586]. The Pd-catalyzed reactions of the 3-stannylcyclobute-nedione 718 with iodobenzene, and benzoyl chloride[587], and alkenylation with alkenyl(phenyl)iodonium triflates proceed smoothly by the co-catalysis by Cul[588,589],... 

Direct C-l deprotonation-lithiation occurs on treatment of the O-benzyl-ated or -silylated glycals with strong bases such as tert-butyllithium at low temperatures, and the vinyllithiums (such as 120) can subsequently be stannylated with tributylstannyl chloride.135 Otherwise, compound 121 can be produced from S-phenyl tetra-C-benzyl-l-thio-/f-D-glucopyranoside via sulfone 122 by treatment with tributylstannane and a radical initiator.132... 

Tellurobenzaldehyde Adduct2 1.4 ml of a solution (1.0M) of trimethylaluminum (1.4 mmol) in hexane are added to a solution of424 mg (0.6 mmol) ofbis [tributylstannyl] tellurium in 10 ml toluene under argon. The mixture is stirred at 90 for 15 h. The toluene is carefully removed under reduced pressure. 15 ml dioxane, 246 mg (3.0 mmol) cta-2,3-dimethyl-l,3-butadiene, and 106 mg (1.0 mmol) benzaldehyde are added in sequence to the residue. The mixture is refluxed for 6 h and then poured into water. The product, 4,5-dimethyl-2-phenyl-3,6-dihydro-2H-tetturine, was obtained after the usual work-up and flash-chromatography on alumina with hexane/dichloromcthanc (5 1) as the mobile phase yield 49%. 

Poly[(i )-2-bromo-5-(tributylstannyl)-3-l4-(4-ethyl-2-oxazolin-2-yl)-phenyl]thiophene [Polymerization of (i )-2-bromo-5-(tributylstannyl)-3-[4-(4-ethyl-2-oxazolin-2-yl)phenyl]thiophene (EOPT-Br,Sn) with Pd2(dba)3 as a catalyst, the CuO-modified Stille-McCullough method] [74]. 

Alkyl stannyl selenides are also useful nucleophilic selenium reagents. Tri-methylstannyl or tributylstannyl methyl selenides 58 react with halides 59 to produce unsymmetrical selenides 60 in good yields in the presence of a fluoride ion or by treatment with n-butyllithium (Scheme 44) [84]. Tributylstannyl phenyl selenide (61) reacts smoothly with acetals to give monoselenoacetals 62 in the presence of boron trifluoride etherate (Scheme 45 a) [85]. Similar reaction conditions were applied to the regioselective ring opening of epoxides (Scheme 45b) [86]. 

A more recent study reached a similar conclusion [78]. It was found that cycliza-tions of (Z)- and ( )-3-phenyl-8-tributylstannyl-6-octenal were highly diastereoselec-tive (Fig. 17). The (Z) isomer yielded cis, fra/js-3-phenyl-2-vinylcyclohexanol as the major product (96 4) whereas the (E) isomer afforded the trans, trans isomer (95 5). A favorable HOMO-LUMO interaction was proposed as a decisive factor in stabilizing the favored synclinal transition states. This stabilization is lacking in the alternative synclinal and antiperiplanar transition states, neither of which has the correct geometry for orbital overlap. As in the previous study, the aldehyde and double bond substituents (asterisked carbons in Fig. 17) are unable to attain an anti orientation in the antiperiplanar transition states, as has been proposed for the intermolecular additions. 

A tributylstannyl group can also be introduced via transmetalation. Collins trans-metalated the trimethylsilyl group of the l,2,4-triazolo[4,3-/>]pyridazine 162 to the corresponding tributylstannane 163 using (Ihi Snj O [35]. Subsequent Stille reaction of 163 with iodobenzene in the presence of Pd(PPh3)4 in DMF at 100°C resulted in the formation of 164, albeit in a low overall yield. In the same paper, a reverse approach was presented in which a brominated triazolopyridazine 165 reacted with 2-tributylstannyl-1,3-oxazole to yield 6-[(l-methyl-l//-l,2,4-triazol-5-yl)methoxy]-7-(l,3-oxazol-2-yl)-3-phenyl[l,2,4]triazolo[4,3-Z ]pyridazine 166 in 37% yield (23% of starting compound was also recovered). 

Electrophilic substitution of 4-(tributystannyl)pyridazines, prepared from tributylstannyl acetylenes and tetrazines, has been demonstrated (Scheme 80) with iodination, and palladium-catalyzed benzoylation and phenylation <91H(32)1387>. 

The Pd°-catalyzed coupling reaction of j5-5-iodo-2 -deoxy-3, 5 -di-0-acetyluridine with 2-trimethylstannylthiophene and 2-phenyl-5-trimethylstannylthiophene has given the corresponding thiophene substituted nucleosides <91JHC529>. The unprotected 5-iodo-2 -deoxyuridine has also been coupled with 2-(trimethylstannyl)- or 2-(tributylstannyl)thiophene <91JMC2383> a Pd catalyst was used in a coordinating solvent (THE or dioxane), whereas in a noncoordinating solvent (toluene), a Pd° catalyst was found to be essential. 

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