Tributylstannylation

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]. 

Other approaches to (36) make use of (37, R = CH ) and reaction with a tributylstannyl allene (60) or 3-siloxypentadiene (61). A chemicoen2ymatic synthesis for both thienamycia (2) and 1 -methyl analogues starts from the chiral monoester (38), derived by enzymatic hydrolysis of the dimethyl ester, and proceeding by way of the P-lactam (39, R = H or CH ) (62,63). (3)-Methyl-3-hydroxy-2-methylpropanoate [80657-57-4] (40), C H qO, has also been used as starting material for (36) (64), whereas 1,3-dipolar cycloaddition of a chiral nitrone with a crotonate ester affords the oxa2ohdine (41) which again can be converted to a suitable P-lactam precursor (65). 

Triazole-4,5-dicarboxylic acid, 2-(tributylstannyl)-, diethyl ester... 

From a tributylstannyl phosphate BnBr, Et4N Br , CH3CN, reflux. Phenacyl, 4-nitrobenzyl, and simple alkyl derivatives were similarly prepared. Yields are substrate and alkylating-agent dependent. ... 

Butynoate 29a reaeted with hexabutylditin in the presenee of PdCl2(PPh3)2 to give the 2,3-bis(tributylstannyl)aerylate 30a in nearly quantitative yield. But 30a eould not be eonverted to the 3,4-bis(tributylstannyl)-2(5//)-furanone 31. However, the analogous THP-proteeted bis(stannate) 30b prepared by a similar proee-dure reaeted with aeidie ion-exehange resin in methanolie solution the hydroxylie group of 30b was deproteeted and eyelization oeeurred to furnish the furanone 31 (Seheme 11) (99JOC328). 

Bromo atom of ethyl (3S)-10-bromo-3-methyl-7-oxo-2,3-dihydro-7//-pyrido[l,2,3- fe]-l,4-benzothiazine-6-carboxylate was change for hetaryl groups with tributylstannyl derivatives of heterocycles in the presence of (Ph3P)2Pd(II)Cl2 in boiling toluene (OOMIPIO). 7-Aryl-5-oxo-2,3-dihydro-5//-pyrido[l,2,3- fe]-l,4-benzothiazine-6-carboxylates, 6-carboxamides and their 1,1-dioxide derivatives were prepared from 7-chloro derivatives in the... 

Z)-3-(Tributylstannyl)allylamine participates in a palladium-catalyzed cross-coupling reaction with 2-bromobenzaldehyde (73, R = H) to give 3//-2-benzazepine (75, R = H). A similar reaction with the corresponding acetophenone 73 (R = Me) produces 1 -methyl-3//-2-benzazepine (75 R = Me), whereas with ethyl 2-bromobenzoate (73, R = OMe), 3//-2-benzazepin-(12/7)-one (74) is formed.237... 

Ally 1(trialky 1)- and allyl(triaryl)stannanes react with aldehydes and electron-deficient ketones on heating to give homoallylic alcohols48, although rather high temperatures are required. 2-Methylene-l,3-bis(tributylstannyl)propane is somewhat more reactive49-50, as are allyltin halides, which can be used in the presence of water51. 

Several trialkoxy(2-butenyl)zirconium(IV)6,7i 18 and 2-butenylbis(cyclopentadienyl)zirco-nium(IV)18,19 124 complexes have been investigated with respect to the diastereoselectivity on addition to aldehydes. Chlorobis(cyclopentadienyl)-(3-tributylstannyl-2-propenyl)zirconium(IV), prepared by hydrozirconation of tributyl-(l,2-propadienyl)tin, accomplishes the (E)-selective, Wittig-like 1,2-propenylidenation of aldehydes and methyl ketones125. 

Iodoquinoxaline and 4-methyl-5-tributylstannyl-l,3-dithiol-2-one gave 2-(2-0X0-5 -methyl-1,3 -dithiol-4-yl)quinoxaline (63) (l-methyl-2-pyrrolidinone, 5°C, CuTC i, A, 40 min 44%). ... 

The polymeric organotin carbonate is less volatile than the oxide and, in this connection, tris(tributylstannyl) phosphate, (Bu3Sn)3P04, which is likely to have a similarly self-associated structure [cf., (MejSn)3(P04)2-8 HjO (593)], is also being used as a wood preservative (533) in Holland. 

C2JH49N3OJS 80082-62-8) see Aztreonam 2-(tribUtylstannyl)vinyl ethyl ether (C H340Sn 20420-43-3) see Fluvastatin sodium tributyltin azide... 

The synthesis of different substituted finans by cyclization of 4-pentynones using potassium tert-butoxide in DMF was reported <96TL3387>. Dihydrofuran 32 can be prepared by a destannylative acylation of l-[(2-methoxyethoxy)methoxy]-2-(phenylsulfonyl)-2-(tributylstannyl)-cyclopropane. Treatment of 32 with BFj-EtjO yields 3-acyUurans via an intramolecular Prins-type reaction of the resulting oxonium ion intermediate <96TL4585>. 

Stille cross coupling reactions usually proceed under mild neutral conditions. 2-Substituted thiazoUnes can be obtained by the cross coupling reaction of 2-bromothiazolines with various tributylstannyl compounds. Previous attempts at a palladium mediated coupling of 2-trimethylstannylthiazoUne led to only decomposition of the substrate <96TL4857>. 

Lithio-l,3-dioxanes are prepared by reductive lithiation of 4-(phenylthio)-l,3-dioxanes and by transmetallation of the corresponding 4-(tributylstannyl)-l,3-dioxanes. This section describes the use of 4-lithio-l,3-dioxanes in the synthesis ofsyn- and anfz-l,3-diols. 

The closely related tributylstannyl nitronates 1120, which can be expected to react in the same way as O-silylnitronates, have been prepared by treatment of aliphatic nitro compounds 1035 with tributylstannylamine 1118 at 24°C or by heating of 1035 with tributylstannyl oxide 1119 in toluene with azeotropic removal of H2O [160] (Scheme 7.49). 

The IR-spectra of a mixture of propyl chloride/tributylstannyl 2-methylpro-panoate (the saturated analogs of vinyl chloride/TBSM) analogous to vinyl chloride and TBSM units in their copolymer revealed the formation of coordination bonds... 

A considerable viscosity increase in copolymers of tributylstannyl methacrylate with methyl methacrylate, butyl acrylate and styrene upon prolongated storage has been observed and special agents to eliminate this effect have been proposed 108). It is likely that the destruction of intermolecular coordination complexes formed by involvement of tin and carbonyl groups in comonomer units takes place in this case. 

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