A chiral [2]catenane precursor of the antiarthritic gold(I) drug auranofin
A chiral [2]catenane precursor of the antiarthritic gold(I) drug auranofin
复制标题
DOI：
10.1002/anie.200503431
复制
发表时间：
2006-01-01
影响因子：
16.6
通讯作者：
Che, CM
中科院分区：
文献类型：
--
作者：
Chui, SSY;Chen, R;Che, CM
分子金(i)[2]链烷的自组装形成是已知的。例如，据报道，金 (i) 叔丁基乙炔化物、[1a] 二乙炔化物、[1b–f] 和硫醇盐络合物 [2] 在没有辅助配体或具有空间不受阻碍的辅助配体的情况下会生成联锁金属环，这些金属环通过弱 AuI… AuI 相互作用而稳定。 [3]在这些配合物中，均配金 (i) 硫醇盐因其光物理 [4] 和抗关节炎特性而受到了我们的关注。 [5]然而，大多数具有芳香族或脂肪族取代基的均配金(i)硫醇盐在常见有机溶剂中的溶解度较低。此外，它们通常形成环状或聚合结构[6, 7]，或者它们的固态结构未知。口服抗关节炎药物金诺芬的前体，即2,3,4,6-四-O-乙酰基-β-1-d-吡喃硫代葡萄糖酸-S金(i)，是一种非芳香族均配金(i)硫醇盐，其手性 糖基化硫醇配体可能赋予其药用特性。尽管金诺芬 [(PEt3) Au (SR)][8a] 及其氧化产物 [(PEt3) 4Au4 (SR) 2](NO3) 2 [8b](RSH= 2, 3, 4, 6-tetra-O-乙酰基-β-1-d-硫代葡萄糖) 的结构已确定，但尚无关于 [{Au (SR)} n]（前体）的结构信息 制备临床使用的金诺芬的原料。在此，我们描述了一种前所未有的糖基化金(i)硫醇盐的结构，即undeca {2, 3, 4, 6-tetra-O-乙酰基-β-1-dthioglucopyranosato-S gold (i)},[Au11 (SR) 11](1)。除了其独特的结构特征外，这种十一金 (i) 簇在固态和溶液中都表现出有趣的光致发光特性。
The self-assembled formation of molecular gold (i)[2] catenanes is known. For instance, gold (i) tert-butylacetylide,[1a] diacetylide,[1b–f] and thiolate complexes [2] without auxiliary ligands or with sterically unencumbered auxiliary ligands are reported to generate interlocking metallocycles that are stabilized by weak AuI··· AuI interactions.[3] Among these complexes, homoleptic gold (i) thiolates have received our attention because of their photophysical [4] and antiarthritic properties.[5] However, most homoleptic gold (i) thiolates with aromatic or aliphatic substituents have a low solubility in common organic solvents. Also, they usually form cyclic or polymeric structures [6, 7] or their solid-state structures are unknown.The precursor of the orally administrated antiarthritic drug auranofin, namely, 2, 3, 4, 6-tetra-O-acetyl-β-1-d-thioglucopyranosato-S gold (i), is a non-aromatic homoleptic gold (i) thiolate whose chiral glycosylated thiolate ligand may impart its medicinal properties. Although the structures for auranofin [(PEt3) Au (SR)][8a] and its oxidized product [(PEt3) 4Au4 (SR) 2](NO3) 2 [8b](RSH= 2, 3, 4, 6-tetra-O-acetyl-β-1-d-thioglucose) have been determined, there has been no structural information on [{Au (SR)} n]—a precursor material for the preparation of the clinically used auranofin. Herein, we describe the structure of an unprecedented glycosylated gold (i) thiolate, namely, undeca {2, 3, 4, 6-tetra-O-acetyl-β-1-dthioglucopyranosato-S gold (i)},[Au11 (SR) 11](1). Besides its unique structural features, this undecagold (i) cluster displays interesting photoluminescent properties in the solid state and in solution.