(R)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2'-diyl chlorophosphate | 39648-65-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: (R)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2'-diyl chlorophosphate
• 英文别名: (R)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthalene-2,2'-diyl phosphoric acid chloride；13-Chloro-12,14-dioxa-13lambda5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3(8),9,16,18(23)-hexaene 13-oxide；13-chloro-12,14-dioxa-13λ5-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3(8),9,16,18(23)-hexaene 13-oxide
• CAS: 39648-65-2
• 化学式: C₂₀H₂₀ClO₃P
• 分子量: 374.804
• InChiKey: KCWOOURHLYPPAK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2'-diyl chlorophosphate 在 sodium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 13.0h， 以97%的产率得到sodium (R)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2' diyl phosphate
  参考文献：
  名称：

  Chiral rare earth organophosphates as homogeneous Lewis acid catalysts for the highly enantioselective hetero-Diels–Alder reactions

  摘要：

  Various trivalent rare earth-chiral phosphate complexes [(R)-l-RE, (R)-3-RE, and (R)-4-Ce] were prepared and evaluated as a Lewis acid catalyst for the asymmetric hetero-Diels-Alder reaction of aldehydes with the Danishefsky's diene. Some of them effectively promoted the reaction at room temperature in the presence or absence of achiral additives under homogeneous conditions to afford the corresponding cycloadducts with high ee's (up to 99% ee). During these reactions, remarkably high asymmetric amplifications (positive nonlinear effects) were observed as the first example in the metal ion-chiral ligand 1:3 catalytic system. A scandium catalyst bearing the H-8-BNP ligand, (R)-3-Sc, could be recovered after the reaction and successfully reused for the next round of reactions. In addition, the hetero-Diels-Alder reaction of alpha-keto esters was effectively catalyzed by the ytterbium complex, (R)-l-Yb, without any additives thus producing the asymmetric quaternary carbon in excellent enantioselectivities (up to > 99% ee). (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.06.011
• 作为产物：
  描述：

  (R)-5,5',6,6',7,7',8,8'-八氢-[1,1'-联萘]-2,2'-二酚 在 三乙胺 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 (R)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2'-diyl chlorophosphate
  参考文献：
  名称：

  四（磷酸二萘酯或八氢二萘磷酸酯）吡啶鎓（II，II）配合物的合成，结构分析和催化性能

  摘要：

  对映纯（R）-1,1'-联萘和（R）-（5,5'，6,6'，7,7'，8,8制成的Rhho II配合物的X射线结构分析首次出现了'-八氢）联萘磷酸酯配体。还报道了在3,3'-位引入卤素原子的可能性。分离出的铱络合物在对映选择性环丙烷化和Si-H插入反应中作为催化剂（1 mol％）进行了进一步测试，以高收率但中等的对映选择性（ee最大值为63％）提供了手性环丙烷和硅烷。

  DOI：

  10.1021/om300935u

文献信息

• Harvesting New Chiral Phosphotriesters by Phosphorylation of BINOL and Parent Bis-phenols
  作者：G. Argouarch、C. Lalli、A. Ndimba、T. Roisnel

  DOI：10.1055/s-0037-1611295

  日期：2019.2

  were synthesized selectively and in good yields. A systematic study on the phosphorylation of BINOL and other bis-phenols with chlorophosphates is described. An intriguing reactivity has been observed that is attributable to the hydroxyl group acidity and to the leaving group nucleofuge character within the phosphorylating agent used. By playing on these two parameters, new chiral monophosphotriesters

  摘要 系统研究了氯酚磷酸化BINOL和其他双酚的方法。已经观察到令人感兴趣的反应性，其归因于所用的磷酸化剂内的羟基酸度和离去基团的核富勒特性。通过发挥这两个参数，可以选择性地合成高收率的新型手性单磷酸三酯，对称的均聚双酚双磷酸酯和不对称的非均化双酚并入非手性侧链的衍生物。 系统研究了氯酚磷酸化BINOL和其他双酚的方法。已经观察到令人感兴趣的反应性，其归因于所用的磷酸化剂内的羟基酸度和离去基团的核富勒特性。通过发挥这两个参数，可以选择性地合成高收率的新型手性单磷酸三酯，对称的均聚双酚双磷酸酯和不对称的非均化双酚并入非手性侧链的衍生物。
• Synthesis, Structural Analysis, and Catalytic Properties of Tetrakis(binaphthyl or octahydrobinaphthyl phosphate) Dirhodium(II,II) Complexes
  作者：Radim Hrdina、Laure Guénée、Delphine Moraleda、Jérôme Lacour

  DOI：10.1021/om300935u

  日期：2013.1.28

  The X-ray structural analyses of homoleptic Rh(II) complexes made of enantiopure (R)-1,1′-binaphthyl and (R)-(5,5′,6,6′,7,7′,8,8′-octahydro)binaphthyl phosphate ligands are for the first time presented. The possibility to introduce halogen atoms at the 3,3′-positions is also reported. The isolated dirhodium complexes were further tested as catalysts (1 mol %) in enantioselective cyclopropanations and

  对映纯（R）-1,1'-联萘和（R）-（5,5'，6,6'，7,7'，8,8制成的Rhho II配合物的X射线结构分析首次出现了'-八氢）联萘磷酸酯配体。还报道了在3,3'-位引入卤素原子的可能性。分离出的铱络合物在对映选择性环丙烷化和Si-H插入反应中作为催化剂（1 mol％）进行了进一步测试，以高收率但中等的对映选择性（ee最大值为63％）提供了手性环丙烷和硅烷。
• Binaphthol monophosphoric acid derivative and its use
  申请人：Tosoh Corporation

  公开号：EP1038877A1

  公开（公告）日：2000-09-27

  A binaphthol monophosphoric acid derivative of the following formula (1), (2), (3) or (4): wherein each of R1, R2, R3 and R4 which are independent of one another, is hydrogen, a C1-20 linear or branched alkyl group, a C1-20 linear or branched alkenyl group, a C1-20 linear or branched alkynyl group, a phenyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C1-10 linear or branched alkyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C1-10 linear or branched alkenyl group, a phenyl group having its nucleus substituted at the 1-to 4-carbon atom by a C1-10 linear or branched alkynyl group, a naphthyl group or a C3-8 cycloalkyl group, provided that R1 to R4 are not simultaneously hydrogen, wherein each of R5, R6, R7 and R8 which are independent of one another, is hydrogen, a C1-20 linear or branched alkyl group, a C1-20 linear or branched alkenyl group, a C1-20 linear or branched alkynyl group, a phenyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C1-10 linear or branched alkyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C1-10 linear or branched alkenyl group, a phenyl group having its nucleus substituted at the 1-to 4-carbon atom by a C1-10 linear or branched alkynyl group, a naphthyl group or a C3-8 cycloalkyl group.

  下式(1)、(2)、(3)或(4)的二萘酚单磷酸衍生物： 其中相互独立的 R1、R2、R3 和 R4 各为氢、C1-20 直链或支链烷基、C1-20 直链或支链烯基、C1-20 直链或支链炔基、苯基、其核在 1 至 4 碳原子上被 C1-10 直链或支链烷基取代的苯基、在 1 至 4 碳原子处其核被 C1-10 直链或支链烯基取代的苯基、在 1 至 4 碳原子处其核被 C1-10 直链或支链炔基取代的苯基、萘基或 C3-8 环烷基，条件是 R1 至 R4 不同时为氢、 其中相互独立的 R5、R6、R7 和 R8 各为氢、C1-20 直链或支链烷基、C1-20 直链或支链烯基、C1-20 直链或支链炔基、苯基、其核在 1-4 碳原子上被 C1-10 直链或支链烷基取代的苯基、在 1 至 4 碳原子处其核被 C1-10 直链或支链烯基取代的苯基、在 1 至 4 碳原子处其核被 C1-10 直链或支链炔基取代的苯基、萘基或 C3-8 环烷基。
• US6274745B1
  申请人：——

  公开号：US6274745B1

  公开（公告）日：2001-08-14
• Chiral rare earth organophosphates as homogeneous Lewis acid catalysts for the highly enantioselective hetero-Diels–Alder reactions
  作者：Hiroshi Furuno、Tetsuji Hayano、Takeshi Kambara、Yuichi Sugimoto、Takeshi Hanamoto、Yumiko Tanaka、Yong Zhi Jin、Takumi Kagawa、Junji Inanaga

  DOI：10.1016/j.tet.2003.06.011

  日期：2003.12

  Various trivalent rare earth-chiral phosphate complexes [(R)-l-RE, (R)-3-RE, and (R)-4-Ce] were prepared and evaluated as a Lewis acid catalyst for the asymmetric hetero-Diels-Alder reaction of aldehydes with the Danishefsky's diene. Some of them effectively promoted the reaction at room temperature in the presence or absence of achiral additives under homogeneous conditions to afford the corresponding cycloadducts with high ee's (up to 99% ee). During these reactions, remarkably high asymmetric amplifications (positive nonlinear effects) were observed as the first example in the metal ion-chiral ligand 1:3 catalytic system. A scandium catalyst bearing the H-8-BNP ligand, (R)-3-Sc, could be recovered after the reaction and successfully reused for the next round of reactions. In addition, the hetero-Diels-Alder reaction of alpha-keto esters was effectively catalyzed by the ytterbium complex, (R)-l-Yb, without any additives thus producing the asymmetric quaternary carbon in excellent enantioselectivities (up to > 99% ee). (C) 2003 Elsevier Ltd. All rights reserved.