Novel platinum(IV)-carbohydrate complexes: Metal ion coordination behavior of monosaccharides in organic solvents
Novel platinum(IV)-carbohydrate complexes: Metal ion coordination behavior of monosaccharides in organic solvents
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DOI：
10.1021/ja9902726
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发表时间：
1999-07-07
影响因子：
15
通讯作者：
Steinborn, D
中科院分区：
文献类型：
--
作者：
Junicke, H;Bruhn, C;Steinborn, D
[PtMe_3（Me_2CO）（3）] BF_4（1）与一系列异亚丙基保护的碳水化合物L ′在丙酮中反应，合成了新的铂（IV）配位碳水化合物[PtMe_3L] BF_4（14 E-21 E，22 D-24 D）。这些络合反应可伴随着铂促进的异亚丙基裂解（14 E，L' = 1，2; 5，6-二-O-异亚丙基-α-D-呋喃葡萄糖（1A），L = 1，2-O-异亚丙基-α-D-呋喃葡萄糖; 15 E，L' = 3-O-乙酰基-1，2; 5，6-二-O-异亚丙基-α-D-呋喃葡萄糖（2A），L = 3-O-乙酰基-1，2-O-异亚丙基-α-D-呋喃葡萄糖; 16 E，L' = 3-O-（甲磺酰基）-1，2-[5;6-二-O-异亚丙基]-α-D-呋喃葡萄糖（3A），L = 3-O-（甲磺酰基）-1，2-O-异亚丙基-α-D-呋喃葡萄糖：17 E，L' = 1，2; 5，6-二-O-异亚丙基-α-D-呋喃阿洛糖（4A），L = 1，2-O-异亚丙基-α-D-呋喃阿洛糖; 18 E，L ′ = 2，3; 4，6-二-O-异亚丙基-2-酮基-L-古洛糖酸（5A），L = 2，3-O-异亚丙基-2-酮基-L-古洛糖酸; 19E，L ′ = 2，3; 4，6-二-O-异亚丙基-α-L-呋喃山梨糖（6A），L = 2，3-O-异亚丙基-α-L-呋喃山梨糖）。在某些情况下，络合过程中不会损失异丙叉基（14 E，L = L' = 1，2-O-异亚丙基-α-D-呋喃葡糖（10 B）; 15 E，L = L' = 3-O-乙酰基-1，2-O-异亚丙基-α-D;呋喃葡糖（11 B）; 20 E，L = L' = 1，2-O-异亚丙基-α-D-呋喃木糖（12 B），21 E，L = L' = 5，6-O-异亚丙基-D-古洛糖基-γ-内酯（13 B））。此外，具有双保护的碳水化合物配体的配合物22 D-24 D在湿二氯甲烷中经历铂促进的异亚丙基裂解以得到19 E，碳水化合物配体L（7A）裂解以得到[PtMe 3（H2O）（3）] BF 4，并且异亚丙基配体被水配体取代以得到[PtMe 3L（H2O）] BF 4（24 D ′，L = 2，3; 4，5-二-O-异亚丙基β-D-吡喃果糖）。配合物14 E在丙酮中在铂促进的异亚丙基保护基加成中在1周内反应，产生[PtM 3L '] BF 4（25 D，L' = 1，2; 5，6-二-O-异亚丙基-α-D-呋喃葡萄糖）。结果表明，碳水化合物可作为三齿中性配体，具有多种给体中心：3xOH（14 E，17 E-19E），2xOH + O-COMe（15 E），2xOH + O-SO2 Me（16 E），2xOH + O-环（20 E），2xOH + O-缩醛（21 E），1xOH + O-环+O-缩醛（22 D-25 D）.在24 D '中观察到双齿连接（OH + O-环）。制备了在每个糖碳上单独标记C-13的复合物E-14，并且涉及标记碳的J偶联的分析允许分配碳水化合物配体的溶液构象。19E的X射线结构分析（单斜晶系，P2（1），a= 8.607（3）埃，B = 9.955（4）埃，c = 11.415（4）埃，Z = 2）和24 D '（斜方晶系，P2（1）2（1）2（1），a = 9.851（2）埃，B = 11.141（4）埃，c = 20.418（6）埃，Z = 4）在固态中表现出与在溶液中相同的配位，即通过三个羟基，产生一个应变环系统（19 E）和一个五元1，3，2-二氧杂铂环（24 D '）。
New platinum(IV)-coordinated carbohydrate complexes [PtMe3L]BF4 (14E-21E, 22D-24D) have been prepared from the reaction of [PtMe3(Me2CO)(3)]BF4 (1) with a wide range of isopropylidene-protected carbohydrates L'in acetone. These complexation reactions can be accompanied by a platinum-promoted cleavage of an isopropylidene group (14E, L' = 1,2;5,6-di-O-isopropylidene-alpha-D-glucofuranose (1A), L = 1,2-O-isopropylidene-alpha-D-glucofuranose; 15E, L' = 3-O-acetyl-1,2;5,6-di-O-isopropylidene-alpha-D-glucafuranose (2A), L = 3-O-acetyl-1,2-O-isopropylidenel-alpha-D-glucofuranose; 16E, L' = 3-O-(methylsulfonyl)-1,2;5;6-di-O-isopropylidene-alpha-D-glucofuranose (3A), L = 3-O-(methylsulfonyl)-1,2-O-isopropylidene-alpha-D-glucofuranose: 17E, L' = 1,2;5,6-di-O-isopropylidene-alpha-D-allofuranose (4A), L = 1,2-O-isopropylidene-alpha-D-allofuranose; 18E, L' = 2,3;4,6-di-O-isopropylidene-2-keto-L-gulonic acid(5A), L = 2,3-O-isopropylidene-2-keto-L-gulonic acid; 19E, L' = 2,3;4,6-di-O-isopropylidene-alpha-L-sorbofuranose (6A), L = 2,3-O-isopropylidene-alpha-L-sorbofuranose). In some cases, complexation proceeds without the loss of an isopropylidene group (14E, L = L' = 1,2-O-isopropylidene-alpha-D-glucofuranose (10B); 15E, L = L' = 3-O-acetyl-1,2-O-isopropylidene-alpha-D; glucofuranose (11B); 20E, L = L' = 1,2-O-isopropylidene-alpha-D-xylofuranose (12B), 21E, L = L' = 5,6-O-isopropylidene-D-gulono-gamma-lactone (13B)). Furthermore, complexes 22D-24D with diprotected carbohydrate ligands undergo a platinum-promoted cleavage of an isopropylidene group in wet methylene chloride to give 19E, cleavage of the carbohydrate ligand L (7A) to give [PtMe3(H2O)(3)]BF4, and substitution of the isopropylidene ligand by an aqua ligand to give [PtMe3L(H2O)]BF4 (24D', L = 2,3;4,5-di-O-isopropylidene beta-D-fructopyranose), respectively. Complex 14E reacted in acetone within 1 week in a platinum-promoted addition of an isopropylidene protecting group, yielding [PtM3L']BF4 (25D, L' = 1,2;5,6-di-O-isopropylidene-alpha-D-glucofuranose). The results show that carbohydrates can act as tridentate neutral ligands with a wide :variety-of donor sites: 3 x OH (14E, 17E-19E), 2 x OH + O-COMe (15E), 2 x OH + O-SO2Me (16E), 2 x OH + O-ring (20E), 2 x OH + O-acetal (21E), 1 x OH + O-ring + O-acetal (22D - 25D). Bidentate ligation (OH + O-ring) is observed in 24D'. Complexes E-14 singly C-13-labeled at each of the saccharide carbons were prepared, and an analysis of the J couplings involving the labeled carbons permitted an assignment of the solution conformation of the carbohydrate ligand. X-ray structure analysis of 19E (monoclinic, P2(1), a= 8.607(3) Angstrom, b = 9.955(4) Angstrom, c = 11.415(4) Angstrom, Z = 2) and 24D' (orthorhombic, P2(1)2(1)2(1), a = 9.851(2) Angstrom, b = 11.141(4) Angstrom, c = 20.418(6) Angstrom, Z = 4) exhibits the same coordination in the solid state as in solution, namely, via the three hydroxyl groups, yielding a strained-cyclic system (19E) and a five-membered 1,3,2-dioxaplatina ring (24D').