(+)-trans-(2-diphenylphosphino)cyclopentanecarboxylic acid | 130866-09-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+)-trans-(2-diphenylphosphino)cyclopentanecarboxylic acid
• 英文别名: (-)-trans-(2-diphenylphosphino)cyclopentanecarboxylic acid；trans-(2-diphenylphosphino)cyclopentanecarboxylic acid；trans-2-(diphenylphosphino)cyclopentanecarboxylic acid；(1S,2R)-2-diphenylphosphanylcyclopentane-1-carboxylic acid
• CAS: 130866-09-0；130866-12-5；130997-95-4；137134-41-9
• 化学式: C₁₈H₁₉O₂P
• 分子量: 298.321
• InChiKey: LAKBNVJFHGNUIN-IAGOWNOFSA-N

物化性质

• 沸点：
  454.9±38.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.37
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  tert-butyl cyclopent-1-enecarboxylate 在 正丁基锂 、 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 5.5h， 生成 (+)-trans-(2-diphenylphosphino)cyclopentanecarboxylic acid
  参考文献：
  名称：

  Development of chiral phosphine ligands bearing a carboxyl group and their application to catalytic asymmetric reaction

  摘要：

  A new chiral phosphine ligand bearing a carboxyl group, 3-(diphenylphosphino)butanoic acid, was developed and used for palladium catalyzed asymmetric allylic alkylation of cyclic cis-allylic acetates such as 2-cyclopentenyl, 2-cyclohexenyl, and 2-cycloheptenyl acetate. These acetates reacted with triethyl sodiophosphonoacetate in the presence of the palladium catalyst with the ligand to give the corresponding alkylation products in good enantiomeric excesses.

  DOI：

  10.1016/0957-4166(95)00322-g

文献信息

• The first synthesis of chiral phosphinocarboxylic acid ligands, trans-2-(diphenylphosphino)cycloalkanecarboxylic acids. The phosphine-palladium complexes catalyzed asymmetric allylic alkylation
  作者：Yoshiharu Okada、Toru Minami、Yoritaka Sasaki、Yasuo Umezu、Masahiko Yamaguchi

  DOI：10.1016/s0040-4039(00)97502-6

  日期：——

  synthesized chiral phosphinocarboxylic acids were effective as ligand for the palledium-catalyzed asymmetric allylic alkylation of 3-acetoxy-1,3-diphenyl-1-propene and 2-cyclohexenyl acetate with soft carbanion from dimethyl malonate or triethyl phosphonoacetate and sodium hydride to give the alkylation products of up to 83% ee.

  首次合成的手性膦基羧酸有效地用作配位体，用于钯催化的3-乙酰氧基-1,3-二苯基-1-丙烯和2-环己烯基乙酸酯的不对称烯丙基烷基化反应，由丙二酸二甲酯或膦酸三乙酯和氢化钠形成的软碳负离子。烷基化产物的ee最高可达83％。
• Synthesis of a novel type of chiral phosphinocarboxylic acids. The phosphine-palladium complexes catalyzed asymmetric allylic alkylation
  作者：Yoshiharu Okada、Toru Minami、Yasuo Umezu、Shinji Nishikawa、Ryoji Mori、Yutaka Nakayama

  DOI：10.1016/s0957-4166(00)86121-2

  日期：1991.1

  A novel type of chiral cycloalkylphosphines bearing the carboxy group at the beta-position were developed, and used for palladium catalyzed asymmetric alkylation of allylic substrates such as 2-cyclohexenylacetate and 1,3-disubstituted-propenyl acetates (R1CH = CHCH(OAc)R2: R1 = R2 = Ph; R1 = Ph, R2 = (CH2)4OAc; R1 = Ph, R2 = (CH2)6OAc; R1 = Ph, R2 = (CH2)10OAc). Reaction of the propenyl acetates with soft carbon nucleophiles such as triethyl sodiophosphonoacetate and sodiomalonic acid esters in the presence of a palladium catalyst prepared in situ from Pd(OAc)2 and chiral (2-diphenylphosphino)cycloalkanecarboxylic acids (7a,b) gave high yields of alkylation products (PhCH = CHCH(X)Ph: > 77 %ee for X = CH(CO2Et)P(O)(OEt)2 and > 72 %ee for X = CH(CO2Me)2). The alkylation products 15 and 28a-c were converted into optically active alpha-methylene-gamma-lactone and alpha-methylene macrolide derivatives. The high stereoselectivity demonstrated by the chiral phosphinocarboxylic acid-palladium catalyzed allylic alkylation suggested to be caused by an electronic repulsion between the carboxy group on the ligand and the incoming soft carbon nucleophile, which directs the nucleophilic attack on one of the pi-allyl carbons.
• OKADA, YOSHIHARU;MINAMI, TORU;SASAKI, YORITAKA;UMEZU, YASUO;YAMAGUCHI, MA+, TETRAHEDRON LETT., 31,(1990) N7, C. 3905-3908
  作者：OKADA, YOSHIHARU、MINAMI, TORU、SASAKI, YORITAKA、UMEZU, YASUO、YAMAGUCHI, MA+

  DOI：——

  日期：——