Tris(dimethylamino)sulfoniumcyclopentadienide [TAS]+[C5H5]− and Tris(dimethylamino)‐sulfoniumpyrrolide [TAS]+[C4H4N]−: Two Isostructural Salts with “Naked” Anions A− and the “Inverse” Sandwich‐Cations [{(Me2N)3S}2A]+ (A = C5H 5−, C4H4N−)
Tris(dimethylamino)sulfoniumcyclopentadienide [TAS]+[C5H5]− and Tris(dimethylamino)‐sulfoniumpyrrolide [TAS]+[C4H4N]−: Two Isostructural Salts with “Naked” Anions A− and the “Inverse” Sandwich‐Cations [{(Me2N)3S}2A]+ (A = C5H 5−, C4H4N−)
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三(二甲氨基)环戊二烯锍[TAS]+[C5H5]− 和三(二甲氨基)锍吡咯烷[TAS]+[C4H4N]−：两种具有“裸”阴离子 A− 和“反”夹心阳离子 [{( Me2N)3S}2A]+ (A = C5H 5−, C4H4N−)
DOI：
10.1002/anie.199504431
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发表时间：
1995
影响因子：
--
通讯作者：
R. Mews
中科院分区：
文献类型：
--
作者：
Jens Wessel;U. Behrens;E. Lork;R. Mews
通过Bu、NF或类似的有机氟化物裂解Si-C键用于去除Me、Si保护基团，随后形成CH键。在这些反应中的中间体是高度反应性的碳负离子，其在所选择的反应条件下可以从相邻分子中夺取质子。特别适合于Si-元素键断裂的是“TAS-氟化物”（三（二甲基氨基）锍二氟三甲基硅酸盐）[（Me，N），S]+[Me，SiF，]-（I），S '，其容易以无HF形式获得;氟硅酸盐离子的化学行为对应于“裸”氟离子的化学行为。从TAS-氟化物（1）与C、H、SiMe、（2）在CH、CN中在-40 ℃下的反应中，TAS盐3可以以高产率分离为微红色固体[Eq.（a）]。
The cleavage of Si-C bonds by Bu, NF or similar organic fluorides serves to remove Me, Si protective groups with subsequent formation of CH bonds.”] Intermediates in these reactions are highly reactive carbanions, which, under the reaction conditions chosen, can abstract protons from neighboring molecules. Particularly suitable for the cleavage of Si-element bonds is “TAS-fluoride”(tris (dimethy1amino) sulfonium difluorotrimethylsilicate)[(Me, N), S]+[Me, SiF,]-(l),[‘, which is readily available in HF-free form; the chemical behavior of the fluorosilicate ion corresponds to that of a “naked” fluoride ion. 141 From the reaction of TAS-fluoride (1) with C, H, SiMe,(2) in CH, CN at-40 “C, the TAS salt 3 can be isolated in high yield as a reddish solid [Eq.(a)].