糖基铂（IV）配合物的合成、表征及反应活性研究，其中配体为硫代糖。
Synthesis, characterization and reactivity of carbohydrate platinum(IV) complexes with thioglycoside ligands.
机构信息
Institut für Chemie - Anorganische Chemie, Martin-Luther-Universität Halle-Wittenberg, D-06120, Halle, Kurt-Mothes-Strasse 2, Germany.
出版信息
Dalton Trans. 2010 Jul 21;39(27):6327-38. doi: 10.1039/b927058b. Epub 2010 Jun 1.
Reactions of fac-[PtMe3(4,4'-R2bpy)(Me2CO)][BF4] (R = H, 1a; tBu, 1b) and fac-[PtMe3(OAc-kappa2O,O')(Me2CO)] (2), respectively, with thioglycosides containing thioethyl (ch-SEt) and thioimidate (ch-STaz, Taz = thiazoline-2-yl) anomeric groups led to the formation of the carbohydrate platinum(IV) complexes fac-[PtMe3(4,4-R2bpy)(ch*)][BF4] (ch* = ch-SEt, 8-14; ch-STaz, 15-23) and fac-[PtMe3(OAc-kappa2O,O')(ch*)] (ch* = ch-SEt, 24-28; ch-STaz = 29-35), respectively. NMR (1H, 13C, 195Pt) spectroscopic investigations and a single-crystal X-ray diffraction analysis of 19 (ch-STaz = 2-thiazolinyl 2,3,4,6-tetra-O-benzoyl-1-thio-beta-D-galactopyranose) revealed the S coordination of the ch-SEt glycosides and the N coordination of the ch-STaz glycosides. Furthermore, X-ray structure analyses of the two decomposition products fac-[PtMe3(bpy)(STazH-kappaS)][BF4] (21a) and 1,6-anhydro-2,3,4-tri-O-benzoyl-beta-D-glucopyranose (23a), where a cleavage of the anomeric C-S bond had occurred in both cases, gave rise to the assumption that this decomposition was mediated due to coordination of the thioglycosides to the high electrophilic platinum(IV) atom, in non-strictly dried solutions. Reactions of fac-[PtMe3(Me2CO)3][BF4] (3) with ch-SEt as well as with ch-SPT and ch-Sbpy thioglycosides (PT = 4-(pyridine-2-yl)-thiazole-2-yl; bpy = 2,2'-bipyridine-6-yl), having N,S and N,N heteroaryl anomeric groups, respectively, led to the formation of platinum(IV) complexes of the type fac-[PtMe3(ch*)][BF4] (ch* = ch-SEt, 36-40, ch-SPT 42-44, ch-Sbpy 45, 46). The thioglycosides were found to be coordinated in a tridentate kappaS,kappa2O,O, kappaS,kappaN,kappaO and kappaS,kappa2N,N coordination mode, respectively. Analogous reactions with ch-STaz ligands succeeded for 2-thiazolinyl 2,3,4-tri-O-benzyl-6-O-(2,2'-bipyridine-6-yl)-1-thio-beta-D-glucopyranoside (5h) resulting in fac-[PtMe3(ch-STaz)][BF4] (41, ch-STaz = 5h), having a kappa3N,N',N''coordinated thioglycoside ligand.
反应的 fac-[PtMe3(4,4'-R2bpy)(Me2CO)][BF4]（R = H，1a; tBu，1b）和 fac-[PtMe3(OAc-κappa2O，O')(Me2CO)]（2），分别与含有硫乙基（ch-SEt）和硫代咪唑啉（ch-STaz，Taz = 噻唑啉-2-基）的糖苷，导致形成碳水化合物铂（IV）配合物 fac-[PtMe3(4,4-R2bpy)(ch*)][BF4]（ch* = ch-SEt，8-14；ch-STaz，15-23）和 fac-[PtMe3(OAc-κappa2O，O')(ch*)]（ch* = ch-SEt，24-28；ch-STaz = 29-35）。1H、13C、195Pt 核磁共振光谱研究和 19（ch-STaz = 2-噻唑啉基 2,3,4,6-四-O-苯甲酰基-1-硫-β-D-半乳糖吡喃糖苷）的单晶 X 射线衍射分析表明，ch-SEt 糖苷的 S 配位和 ch-STaz 糖苷的 N 配位。此外，两个分解产物 fac-[PtMe3(bpy)(STazH-κS)][BF4]（21a）和 1,6-脱水-2,3,4-三-O-苯甲酰基-β-D-葡萄糖吡喃糖苷（23a）的 X 射线结构分析表明，在这两种情况下都发生了糖苷的键的断裂，这导致了这种分解是由于硫糖苷与高亲电铂（IV）原子的配位引起的，在非严格干燥的溶液中。fac-[PtMe3(Me2CO)3][BF4]（3）与 ch-SEt 以及 ch-SPT 和 ch-Sbpy 硫糖苷（PT = 4-（吡啶-2-基）-噻唑-2-基；bpy = 2,2'-联吡啶-6-基）的反应，分别具有 N，S 和 N，N 杂芳基的糖苷，导致形成类型的铂（IV）配合物 fac-[PtMe3(ch*)][BF4]（ch* = ch-SEt，36-40，ch-SPT 42-44，ch-Sbpy 45，46）。硫糖苷被发现以三齿κS，κ2O，O，κS，κN，κO 和 κS，κ2N，N 配位模式分别配位。与 ch-STaz 配体的类似反应成功地用于 2-噻唑啉基 2,3,4-三-O-苄基-6-O-（2,2'-联吡啶-6-基）-1-硫-β-D-葡萄糖吡喃糖苷（5h），导致形成 fac-[PtMe3(ch-STaz)][BF4]（41，ch-STaz = 5h），具有配位的硫糖苷配体 κ3N，N'，N''。
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