Transmetalation reactions of higher order cyanocuprates: Direct formation of trialkyltin cuprates from tin hydrides which bypasses organolithium intermediates

Total Synthesis of Naturally Configured Pyrrhoxanthin, a Carotenoid Butenolide from Plankton

“…In the first step, the tetrolic ester 24 and (Bu 3 Sn)BuCu(CN)Li 2 [28] underwent the same kind of cishydrostannylation [29] that had been described by Parrain et al for tetrolic acid. [30] Reduction of the resulting unsaturated ester with DIBAH furnished an allylic alcohol in 99 % yield.…”

“…Next, propargyl alcohol (25) was cis-hydrostannylated [31] using (Bu 3 Sn)BuCu(CN)Li 2 . [28] The resulting (tributylstannyl)allyl alcohol (84 % yield) was converted into the known [32] [34] -the heptatrienyldistannane 13 was formed as a 95:5 trans/cis mixture (78 % yield). In addition, an isomeric mixture of heptatrienylmonostannanes was formed in 4 % yield and could not be separated by flash chromatography on silica gel.…”

Total Synthesis of Pseudotrienic Acid B: A Bioactive Metabolite from Pseudomonas sp. MF 381‐IODS

“…Regio-and stereoselective stannylcupration with the mixed higher-order cuprate reagent [(Bu 3 Sn)BuCu(CN)Li 2 ] [11] in the presence of MeOH afforded the two known vinyl stannanes 10 and 11 in a 9:1 ratio with a combined yield of 74 %. These two regioisomers were separated by flash chromatography on silica gel and the desired E vinyl stannane 10 was subjected to iododestannylation to give the known vinyl iodide 12 in very high yield (94 %).…”

Sugar Allyltin Compounds: Preparation and Application in Organic Synthesis

“…This may proceed according to the S N 2 or (to a lesser extent) the S N 2Ј mechanisms and usually provides the primary allyltins. A useful "one-pot" procedure for the synthesis of allyltins from allylic alcohols has been reported by Weigand and Bruckner, [26] whilst an elegant method for the synthesis of the primary allyltins (with a soft tin cuprate reagent [27] ) by the S N 2Ј mechanism was proposed recently. [28] As already mentioned, the methods presented here usually provide the primary allyltin derivatives.…”

“…Pure geometrical isomers of sugar allyltins may be prepared by treatment of the corresponding allylic derivatives with tin nucleophiles, represented by tributyltin cuprate ('Bu 3 SnCuЈ), [27] tributyltin lithium, [5] or tributyltin sodium (Bu 3 SnNa). [45] These nucleophiles may react either in S N 2 or in S N 2Ј modes.…”