（2S，2''S，3S，3''S）-3,3''-二叔丁基-2,2''，3,3''-四氢-2,2''-联苯并[d][1,3]氧杂磷杂戊环 | 1202033-17-7

• 分子结构分类: 有机化合物 - 苯类化合物
• 中文名称: （2S，2''S，3S，3''S）-3,3''-二叔丁基-2,2''，3,3''-四氢-2,2''-联苯并[d][1,3]氧杂磷杂戊环
• 英文名称: BIBOP
• 英文别名: (2S,2'S,3S,3'S)-3,3'-di-tert-butyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[d][1,3]oxaphosphole；(2S,2'S,3S,3'S)-BIBOP；(2S,2'S,3R,3'R)-3,3'-di-tert-butyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[d][1,3]oxaphosphole；(2S,2'S,3S,3'S)-3,3'-Bis(1,1-dimethylethyl)-2,2',3,3'-tetrahydro-2,2'-bi-1,3-benzoxaphosphole；(2S,3S)-3-tert-butyl-2-[(2S,3S)-3-tert-butyl-2H-1,3-benzoxaphosphol-2-yl]-2H-1,3-benzoxaphosphole
• CAS: 1202033-17-7
• 化学式: C₂₂H₂₈O₂P₂
• 分子量: 386.411
• InChiKey: CAVTUIDTRDJLGP-HKDRDPIHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  26
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 、 （2S，2''S，3S，3''S）-3,3''-二叔丁基-2,2''，3,3''-四氢-2,2''-联苯并[d][1,3]氧杂磷杂戊环 以 乙醇 、 二氯甲烷 为溶剂， 反应 0.5h， 以90%的产率得到RuCl₂[(2S,2’S,3R,3’R)-bisdihydrobenzooxaphosphole](p-cymene)
  参考文献：
  名称：

  胺可调谐的钌催化剂，用于酮的不对称还原

  摘要：

  AbstractA series of efficient ruthenium catalysts has been developed for the asymmetric hydrogenation and transfer hydrogenation of ketones with high reactivities and selectivities. The new chiral bisdihydrobenzooxaphosphole (BIBOP)/diamine‐ruthenium complexes catalyzed the enantioselective hydrogenation of substrates such as aryl and heteroaryl cyclic and alkyl ketones with substrate/catalyst (S/C) ratios of up to 100,000. The opposite sense of enantioselectivity can be obtained by proper selection of a diamine with a given chirality of the phosphine. The usefulness of the new system has been demonstrated in the asymmetric hydrogenation of a complex synthetic intermediate towards cholesteryl ester transfer protein (CETP) inhibitors at S/C 20,000 on large‐scale operation.magnified image

  DOI：

  10.1002/adsc.201300727
• 作为产物：
  描述：

  (R)-3-(tert-butyl)-3-oxido-2H-benzo[d][1,3]oxaphosphol-4-yl ((1S,2R,5S)-2-isopropyl-5-methylcyclohexyl) carbonate 在 20% palladium hydroxide on carbon 三氯硅烷 、 水 、 氢气 、 三乙胺 、 potassium hydroxide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 、 正庚烷 、 二氯甲烷 、 乙酸乙酯 、 氯苯 、 甲苯 为溶剂， -78.0~80.0 ℃ 、689.49 kPa 条件下， 反应 31.0h， 生成 （2S，2''S，3S，3''S）-3,3''-二叔丁基-2,2''，3,3''-四氢-2,2''-联苯并[d][1,3]氧杂磷杂戊环
  参考文献：
  名称：

  [EN] NOVEL CHIRAL PHOSPHORUS LIGANDS
  [FR] NOUVEAUX LIGANDS DE PHOSPHORE CHIRAUX

  摘要：

  本发明涉及一系列新颖的具有公式（Ia）和（Ib）的手性磷配体：其中R，1 - rR> 4和X如本文所定义。本发明还涉及用这些手性磷配体制备的手性金属配合物。手性金属配合物可用作实施不对称氢化的催化剂。

  公开号：

  WO2011056737A1

文献信息

• NOVEL CHIRAL PHOSPHORUS LIGANDS
  申请人：Qu Bo

  公开号：US20120277455A1

  公开（公告）日：2012-11-01

  The invention relates to a series of novel chiral phosphorus ligands of formulae (Ia) and (Ib): wherein R, 1-rR>4 and X are as defined herein. The invention also relates to chiral metal complexes prepared with these chiral phosphorus ligands. The chiral metal complexes are useful as catalysts for carrying out asymmetric hydro genation.

  本发明涉及一系列新型手性磷配体，其化学式为（Ia）和（Ib）：其中R，1-rR>4和X的定义如本文所述。本发明还涉及使用这些手性磷配体制备的手性金属配合物。这些手性金属配合物可用作催化剂，用于进行不对称氢化反应。
• Novel, Tunable, and Efficient Chiral Bisdihydrobenzooxaphosphole Ligands for Asymmetric Hydrogenation
  作者：Wenjun Tang、Bo Qu、Andrew G. Capacci、Sonia Rodriguez、Xudong Wei、Nizar Haddad、Bikashandarkoil Narayanan、Shengli Ma、Nelu Grinberg、Nathan K. Yee、Dhileep Krishnamurthy、Chris H. Senanayake

  DOI：10.1021/ol9025815

  日期：2010.1.1

  A series of novel, efficient, air-stable, and tunable chiral bisdihydrobenzooxaphosphole ligands (BIBOPs) were developed for rhodium-catalyzed hydrogenations of various functionalized olefins such as alpha-arylenamides, alpha-(acylamino)acrylic acid derivatives, beta-(acylamino)acrylates, and dimethyl itaconate with excellent enantioselectivities (up to 99% ee) and reactivities (up to 2000 TON).
• US8552212B2
  申请人：——

  公开号：US8552212B2

  公开（公告）日：2013-10-08
• [EN] NOVEL CHIRAL PHOSPHORUS LIGANDS<br/>[FR] NOUVEAUX LIGANDS DE PHOSPHORE CHIRAUX
  申请人：BOEHRINGER INGELHEIM INT

  公开号：WO2011056737A1

  公开（公告）日：2011-05-12

  The invention relates to a series of novel chiral phosphorus ligands of formulae (Ia) and (Ib): wherein R, 1 - rR> 4 and X are as defined herein. The invention also relates to chiral metal complexes prepared with these chiral phosphorus ligands. The chiral metal complexes are useful as catalysts for carrying out asymmetric hydro genation.

  本发明涉及一系列新颖的具有公式（Ia）和（Ib）的手性磷配体：其中R，1 - rR> 4和X如本文所定义。本发明还涉及用这些手性磷配体制备的手性金属配合物。手性金属配合物可用作实施不对称氢化的催化剂。
• Amine-Tunable Ruthenium Catalysts for Asymmetric Reduction of Ketones
  作者：Sonia Rodríguez、Bo Qu、Keith R. Fandrick、Frederic Buono、Nizar Haddad、Yibo Xu、Melissa A. Herbage、Xingzhong Zeng、Shengli Ma、Nelu Grinberg、Heewon Lee、Zhengxu S. Han、Nathan K. Yee、Chris H. Senanayake

  DOI：10.1002/adsc.201300727

  日期：2014.2.10

  AbstractA series of efficient ruthenium catalysts has been developed for the asymmetric hydrogenation and transfer hydrogenation of ketones with high reactivities and selectivities. The new chiral bisdihydrobenzooxaphosphole (BIBOP)/diamine‐ruthenium complexes catalyzed the enantioselective hydrogenation of substrates such as aryl and heteroaryl cyclic and alkyl ketones with substrate/catalyst (S/C) ratios of up to 100,000. The opposite sense of enantioselectivity can be obtained by proper selection of a diamine with a given chirality of the phosphine. The usefulness of the new system has been demonstrated in the asymmetric hydrogenation of a complex synthetic intermediate towards cholesteryl ester transfer protein (CETP) inhibitors at S/C 20,000 on large‐scale operation.magnified image