Carbohydrate-based phosphines as supporting ligand for palladium-catalyzed Suzuki–Miyaura cross-coupling reaction

Synthesis of a New Carbohydrate-Derived Chiral Phosphine and Its Coordinating cis- and trans-Pt(II) Complexes

“…为了制备 5, 首先尝试了 2 与丁基锂反应夺去 2-位 羟基上的氢原子形成氧负离子, 再与 MeI 在室温下反应 (Scheme 1), TLC 发现有极性大、可能是季膦盐的产物, 没有发现目标产物. 而用 NaH 夺氢再与 MeI 反应, 可分 到所需要的产物但产率较低(23%), 也有大量的季膦盐 形成 [12] . 这些数据表明: (1)…”

“…通过环 氧物开环反应可将 Ph 2 P -负离子引入到立体位阻较大的 糖环二级碳上 [5,6] , 且高产率地制得甲基 3-脱氧-3-二苯 膦基-4,6-氧-苯次甲基-α-D-吡喃阿糖苷 (2). 手性膦 2 是多种过渡金属的多功能配体 [7 ～ 10] , 可在钯催化的 Heck 和 Suzuki 反应中作为高性能的支持配体 [11,12] . 在 表征 2 结构时发现碳水化合物的手性对磷原子周围的空 间影响比较大、导致磷上的 2 个苯环是不等价的 [5] , 从 而提供了一个利用碳水化合物单元的手性诱导产生磷 原子手性进而制得 P-手性膦的机会.…”

Structure‐Activity Relationships of Glucose‐based PdII‐Bis(NHC) Complexes in a Model Suzuki‐Miyaura Reaction

“…[7] Natural chiral pools such as amino acids have also been explored. [8] However, even though carbohydrates are the most ubiquitous class of biomolecules, they have only rarely been used in coordination chemistry, with only a few known examples of phosphine- [9] and NHC-ligands [10] incorporating a carbohydrate moiety. Besides the important factor of sustainability, carbohydrate-based NHC complexes have an increased water solubility [11] and are expected to exhibit a lower toxicity, since similar trends are found in biomolecule-bearing imidazolium based ionic liquids.…”

Structure-Activity Relationships of Glucose-based PdII-Bis(NHC) Complexes in a model Suzuki-Miyaura Reaction

“…4 Natural chiral pools such as amino acids have also been explored. 5 However, even though carbohydrates are the most ubiquitous class of biomolecules, they have only rarely been used in coordination chemistry, with only a few known examples of phosphine- 6 and NHC-ligands 7 incorporating a carbohydrate moiety. Besides the important factor of sustainability, carbohydrate-based NHC complexes have an increased water solubility 8 and are expected to exhibit a lower toxicity, since similar trends are found in biomolecule-bearing imidazolium based ionic liquids.…”