(R)-2((R)-1,1'-binaphthyl-2'-hydroxy-2-oxy)-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepine

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-2((R)-1,1'-binaphthyl-2'-hydroxy-2-oxy)-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepine
• 英文别名: 2'-(dinaphtho[2,1-d:1',2'-f][1,3,2]dioxa-phosphepin-4-yloxy)-1,1'-binaphthyl-2-ol；2'-[Dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-yloxy]-1,1'-binaphthalene-2-ol；1-[2-(12,14-dioxa-13-phosphapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-yloxy)naphthalen-1-yl]naphthalen-2-ol
• 化学式: C₄₀H₂₅O₄P
• 分子量: 600.61
• InChiKey: AMNDSCWHYXHMRI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.5
• 重原子数：
  45
• 可旋转键数：
  3
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  55.7
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-2((R)-1,1'-binaphthyl-2'-hydroxy-2-oxy)-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepine 、 N,O-双三甲硅基乙酰胺 以 氯仿 为溶剂， 反应 1.0h， 以90%的产率得到(R)-2-((R)-1,1'-binaphthyl-2'-trimethylsilanoxy-2-oxy)-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepine
  参考文献：
  名称：

  Facile one-pot synthesis of BINOL- and H8-BINOL-based aryl phosphites and their use in palladium catalysed asymmetric allylation

  摘要：

  Novel P-monodentate aryl phosphite ligands have been synthesised in one step from (R)-BINOL, (R)-H-8-BINOL and (R)-H-8-3, 3'-dibromo-BINOL. With the new aryl phosphites, up to 86% ee was observed in the asymmetric Pd-catalysed amination of 1,3-diphenyl-2propenyl acetate with sodium diformylamide. In the enantioselective alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate, up to 97% enantioselectivity was achieved. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.08.046
• 作为产物：
  描述：

  (R)-1,1'-Bi-2-naphthol 在 三乙胺 、 三氯化磷 作用下， 以 苯 为溶剂， 以92%的产率得到(R)-2((R)-1,1'-binaphthyl-2'-hydroxy-2-oxy)-dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepine
  参考文献：
  名称：

  Facile one-pot synthesis of BINOL- and H8-BINOL-based aryl phosphites and their use in palladium catalysed asymmetric allylation

  摘要：

  Novel P-monodentate aryl phosphite ligands have been synthesised in one step from (R)-BINOL, (R)-H-8-BINOL and (R)-H-8-3, 3'-dibromo-BINOL. With the new aryl phosphites, up to 86% ee was observed in the asymmetric Pd-catalysed amination of 1,3-diphenyl-2propenyl acetate with sodium diformylamide. In the enantioselective alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate, up to 97% enantioselectivity was achieved. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.08.046

文献信息

• Iridium-Catalyzed Asymmetric Borylation of Unactivated Methylene C(sp³)–H Bonds
  作者：Ronald L. Reyes、Tomohiro Iwai、Satoshi Maeda、Masaya Sawamura

  DOI：10.1021/jacs.9b01952

  日期：2019.5.1

  Herein, we show the highly enantioselective borylation of unactivated methylene C(sp3)-H bonds in 2-alkylpyridines and 2-alkyl-1,3-azole derivatives using an iridium-BINOL-based chiral monophosphite catalyst system. Quantum chemical calculations using the artificial force induced reaction (AFIR) method suggested that a monophosphite-Ir-tris(boryl) complex generates a narrow chiral reaction pocket where

  在此，我们展示了使用基于铱-BINOL 的手性单亚磷酸酯催化剂体系对 2-烷基吡啶和 2-烷基-1,3-唑衍生物中未活化的亚甲基 C(sp3)-H 键的高度对映选择性硼化。使用人工力诱导反应 (AFIR) 方法进行的量子化学计算表明，单亚磷酸盐-Ir-三（硼基）配合物会产生一个狭窄的手性反应袋，其中对映体亚甲基 CH 键的分化是通过多个非共价相互作用的组装完成的。
• Diastereoisomeric bisphosphite ligands in the hydroformylation of octenes: rhodium catalysis and HP-NMR investigations
  作者：Detlef Selent、Wolfgang Baumann、Klaus-Diether Wiese、Armin Börner

  DOI：10.1039/b814120g

  日期：——

  Diastereoisomeric hydroformylation catalysts show differences for the catalyst preformation pathway and a strongly reduced n-octene hydroformylation activity for the (S,S,R)-isomer.

  非对映异构体加氢甲酰化催化剂在催化剂预形成途径上存在差异，而 (S,S,R)-异构体的正辛烯加氢甲酰化活性则大大降低。
• Asymmetric Pd-catalyzed allylic amination of 1,3-diphenylallyl acetate with dipropylamine in ionic and molecular solvents
  作者：S. E. Lyubimov、V. A. Davankov、A. S. Kucherenko、S. G. Zlotin、S. V. Zheglov、K. N. Gavrilov、P. V. Petrovskii

  DOI：10.1007/s11172-006-0155-9

  日期：2005.11

  Asymmetric catalytic allylic amination of 1,3-diphenylallyl acetate with dipropylamine in an ionic liquid, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, and in THF and CH2Cl2 in the presence of palladium complexes of P-monodentate phosphite and phosphoramidite derivatives of S-1,1′-bis-2-naphthol was carried out. This gave a product with ee of up to 65%. The level of asymmetric induction is retained after three catalyst cycles.

  在离子液体 1-丁基-2,3-二甲基咪唑鎓四氟硼酸盐中，以及在 THF 和 CH2Cl2 中，在 S-1,1′-双-2-萘酚的亚磷酸 P-monodentate 和亚磷酰胺衍生物的钯络合物存在下，进行了 1,3-二苯基烯丙基乙酸酯与二丙胺的不对称催化烯丙基胺化反应。这样得到的产品ee高达 65%。经过三次催化剂循环后，不对称诱导水平得以保持。
• Gavrilov, K. N.; Mikhel', I. S., Russian Journal of Inorganic Chemistry, <hi>1994</hi>, vol. 39, p. 439 - 441
  作者：Gavrilov, K. N.、Mikhel', I. S.

  DOI：——

  日期：——
• Facile one-pot synthesis of BINOL- and H8-BINOL-based aryl phosphites and their use in palladium catalysed asymmetric allylation
  作者：Konstantin N. Gavrilov、Sergey E. Lyubimov、Pavel V. Petrovskii、Sergey V. Zheglov、AntonS. Safronov、Roman S. Skazov、Vadim A. Davankov

  DOI：10.1016/j.tet.2005.08.046

  日期：2005.10

  Novel P-monodentate aryl phosphite ligands have been synthesised in one step from (R)-BINOL, (R)-H-8-BINOL and (R)-H-8-3, 3'-dibromo-BINOL. With the new aryl phosphites, up to 86% ee was observed in the asymmetric Pd-catalysed amination of 1,3-diphenyl-2propenyl acetate with sodium diformylamide. In the enantioselective alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate, up to 97% enantioselectivity was achieved. (c) 2005 Elsevier Ltd. All rights reserved.