Stannane hydrolyzate

Alternatively, 138 can be converted to CBZ carbamate 142 using standard conditions (Scheme 4.30). This 5-bromoisoindoline was transformed to stannane 143 in one step with bistributyltin in the presence of a palladium catalyst. The stannane was treated with 136 under Stille conditions to afford coupled product 144. The resulting ester was hydrolyzed with sodium hydroxide, and the CBZ group was removed under hydrogenolysis conditions to deliver garenoxacin (4) (Hayashi et al., 2002). 

Hydrolysis of the nrrahydrides. Silane hydrolyzes in the presence of catalytic amounts of hydroxide. In contrast, methane, germane. and stannane do not hydrolyze even in the presence of large amounts of hydroxide ion. 

The higher germanes are obtained by electric discharge through GeH4. The flammability of the germanes is less than that of the silanes, and they do not hydrolyze. Stannane can be prepared by the reaction... 

Metal triorganostannides (R = Et, n-Bu, Ph, etc.) are hydrolyzed to the parent stannanes. Alkali-metal derivatives react ... 

The trimethylstannoxy methoxy tellurium tetrafluorides hydrolyze in moist air with loss of trimethyl(hydroxy)stannane. ... 

This aUows the cross-coupling of an aryUialide (2) with an aryltrialkyl stannane in presence of a boronic ester. The latter remains unreactive because it would need to be hydrolyzed to a boronate to be suited for Pd-mediated couplings. Progression in a couphng cycle would further require OH , CO , or F , not present under the used StiUe couphng conditions [178,179]. The Stille conditions proved very useful for affording many aryl-aryl [1, 4, 180, 181, 182], vinyl-aryl [9, 161, 183, 184] and also aUcyl-aryl [185] compounds bearing hydrolytically labile moieties. The commonly used reactivities of aryl or vinyl halide components are like those in the... 

The reaction of fluoromethyl phenyl sulfone with diethyl chlorophosphate at room temperature requires the use of 2 eq of base ( -BuLi, LDA, LiHMDS) to give the lithium salt of diethyl 1-(phenylsulfonyl)-l-fluoromethylphosphonate, which can be hydrolyzed and isolated in 73% yield or reacted in situ with a large variety of carbonyl compounds to form the corresponding a-fluorovinyl phenyl sulfones in moderate to good yields (44-95%, Scheme 3.9). - These sulfones are readily converted into 1-fluoroalkenes via the corresponding (fluorovinyl)stannanes. ... 

In the second step the C-2 dienic chain was attached and the resulting amide was treated with ( )-2-(tributylstannyl)ethenyllithium, prepared from the corresponding bis-stannane [105]. The vinyltin derivative was succesfully coupled with the y-bromodienamide, but the ketal function could not be hydrolyzed to the corresponding final ketone (Scheme 31). 

A mixture of POCI3, startg. stannane, and N-phenyl-N-methylformamide heated to 70° for 3 h, and hydrolyzed - p-methoxybenzaldehyde. Y 96%. Interestingly, the method is also applicable to unsubst. and deactivated aryl derivs. F.e.s. W.P. Neumann et al.. Tetrahedron 45, 951-60 (1989). 

One of the earliest methods for preparing aromatic boronic acids involved the reaction between diaryl mercury compounds and boron trichloride [198]. As organomer-curial compounds are to be avoided for safety and environmental reasons, this old method has remained unpopular. In this respect, trialkylaryl silanes and stannanes are more suitable and both can be transmetallated efficiently with a hard boron halide such as boron tribromide [199]. The apparent thermodynamic drive for this reaction is the higher stability of B-C and Si(Sn)-Br bonds of product compared to the respective B-Br and Si(Sn)-C bonds of substrates. Using this method, relatively simple arylboronic acids can be made following an aqueous acidic workup to hydrolyze the arylboron dibromide product [193]. For example, some boronic acids were synthesized more conveniently from the trimethylsilyl derivative than by a standard ortho-metallation procedure (entry 11, Table 1.3). 

A soln. of di-n-butyltin dichloride in dry ether added dropwise with stirring during 1 hr. to a soln. of 2,2 -dilithiumbiphenyl (prepared in 86-91% yield from 2,2 -dibromobiphenyl and Li-chips in dry ether under Ng), stirring continued 2 hrs. at room temp., then hydrolyzed with HgO-satd. ether 5,5-di-n-butyl-dibenzostannol. Y 64.8%. F. e., also synthesis of non-cyclic stannanes, s. R. Gelius, B. 93, 1759 (1960). 

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