2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetrahydro-4,4'-bioxazole

• 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: 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetrahydro-4,4'-bioxazole
• 英文别名: (4S,4'S)-2,2'-Bis(2-fluorophenyl)-4,4',5,5'-tetrahydro-4,4'-bioxazole；(4S)-2-(2-fluorophenyl)-4-[(4S)-2-(2-fluorophenyl)-4,5-dihydro-1,3-oxazol-4-yl]-4,5-dihydro-1,3-oxazole
• 化学式: C₁₈H₁₄F₂N₂O₂
• 分子量: 328.318
• InChiKey: BGEBBOLRVOCQDU-HZPDHXFCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetrahydro-4,4'-bioxazole 在 palladium 10% on activated carbon 、 氢气 、 sodium hydride 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 20.0h， 生成 2,2'-((4S,4'S)-4,4',5,5'-tetrahydro-4,4'-bioxazole-2,2'-diyl)diphenol
  参考文献：
  名称：

  酒石酸的新型O，N，N，O-四齿配体

  摘要：

  从1-酒石酸合成了一类新的高度稳定的O，N，N，O-四齿生物恶唑啉配体。在钯催化的不对称烯丙基烷基化反应中对那些配体的探索产生了烷基化产物，其ee高达96％。还证明了额外的螯合以获得高对映选择性的必要性。此配体的结构修饰可能会导致从廉价的手性库中鉴定出一种新型的优先手性配体。

  DOI：

  10.1016/j.tet.2013.05.049
• 作为产物：
  描述：

  5,10-bis<4-(N-(9-fluorenylmethoxycarbonyl)-L-alanylamino)phenyl>-15,20-bis<4-(2',3',4',6'-tetra-O-acetyl-β-D-glucopyranosyloxy)phenyl>porphyrin 在 甲基磺酰氯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以59%的产率得到2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetrahydro-4,4'-bioxazole
  参考文献：
  名称：

  C₂-Symmetric Bisphosphinobioxazoline as a Chiral Ligand. Highly Enantioselective Palladium-Catalyzed Allylic Substitutions and Formation of P,N,N,P Tetradentate Palladium (II) Complexes

  摘要：

  The C-2-symmetric bisphosphinobioxazoline [(S,S)-Phos-Biox] 4 was found to be a highly efficient chiral ligand for Pd-catalyzed enantioselective allylic substitution of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate and afforded enantioselectivities of up to 97% ee. Moderate enantioselectivities have been observed in Pd-catalyzed desymmetrizations of cis-1,4-bis(benzoyloxy)-cyclopent-2-ene (12) with dimethyl malonate (51-78% yield, 38-58% eel) and N-benzyl-N-methylamine (87% yield, 33% ee) nucleophiles and of biscarbamate 15 of cis-1,4-dihydroxycyclopent-2-ene (90% yield, 50% ee). A 1:1 molar mixture of(S,S)-Phos-Biox 4 with Pd(CH3CN)(2)Cl-2 and [(eta(3)-C3H5)PdCl](2) afforded the P,N,N,P-tetradentate Pd(II) complexes 19a and 19b, respectively. The structures of the complexes 19a,b were determined by X-ray analysis. The complex 19a also exhibited high enantioselectivity (86% yield, 92% ee) in allylic substitution of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate.

  DOI：

  10.1021/jo990126i

文献信息

• A new C2-symmetric chiral bisphosphine ligand containing a bioxazole backbone: highly enantioselective hydrosilylation of ketones
  作者：Sang-gi Lee、Chung Woo Lim、Choong Eui Song、In O Kim

  DOI：10.1016/s0957-4166(97)00554-5

  日期：1997.12

  C2-Symmetric (4S,4′S)-2,2′-bis(o-diphenylphosphinophenyl)-4,4′,5,5′-tetrahydro-4,4′-bi(1,3-oxazole) (1, Phos-Biox) has been designed and synthesized as a chiral ligand for metal-catalyzed reactions. The Phos-Biox 1 was found to be an efficient ligand for rhodium(I)-catalyzed asymmetric reduction of prochiral acetophenones with diphenylsilane to give optically active secondary alcohols of up to 97% ee

  C 2-对称的（4 S，4 'S）-2,2'-双（邻-二苯基膦基苯基）-4,4'，5,5'-四氢-4,4'-bi（1,3-恶唑） （1，Phos-Biox）已被设计和合成为金属催化反应的手性配体。发现Phos-Biox 1是铑（I）催化的手性苯乙酮与二苯基硅烷的不对称还原的有效配体，可提供高达97％ee的旋光仲醇。
• Palladium Catalyzed Asymmetric Allylation of 3-OBoc-Oxindoles: An Efficient Synthesis of 3-Allyl-3-hydroxyoxindoles
  作者：Samydurai Jayakumar、Nandarapu Kumarswamyreddy、Muthuraj Prakash、Venkitasamy Kesavan

  DOI：10.1021/acs.orglett.5b00034

  日期：2015.3.6

  synthesized in very good enantio- (up to 97% ee) and diastereoselectivities (dr up to 7.6:1) with contiguous quaternary and tertiary stereogenic centers by employing tartrate derived bi(oxazoline) in Pd-catalyzed allylation of 3-OBoc-oxindole. Synthetic utility of 3-allyl-3-hydroxyoxindole was demonstrated by synthesizing a highly substituted spiro(oxindole-3,2′-tetrahydrofuran) derivative in good yield and

  通过酒石酸衍生的双（恶唑啉）在钯催化下，以连续的季和叔立体中心，以非常好的对映体（高达97％ee）和非对映选择性（dr高达7.6：1）合成3-烯丙基-3-羟基恶吲哚。 3-OBoc-羟吲哚的烯丙基化。通过以高产率和立体选择性合成高度取代的螺（oxindole-3,2'-四氢呋喃）衍生物，证明了3-烯丙基-3-羟基羟吲哚的合成效用。
• Palladium-catalyzed asymmetric allylic alkylation of 3-amino-2-oxindoles: Synthesis of 3-allyl-3-amino-2-oxindoles
  作者：Nandarapu Kumarswamyreddy、Samydurai Jayakumar、Venkitasamy Kesavan

  DOI：10.1016/j.tetlet.2021.153385

  日期：2021.10

  bi(oxazoline) ligand with palladium (II) species catalyzed asymmetric allylic alkylation reaction to access highly valuable 3-allyl-3-amino-2-oxindoles with vicinal quaternary and tertiary stereocenters in very good yields (up to 91%) and excellent enantioselectivity (up to 98% ee) with moderate to good diastereoselectivity (up to 5:1). The synthetic utility of 3-allyl-3-amino-2-oxindole was further

  酒石酸衍生的双（恶唑啉）配体与钯 (II) 物质催化不对称烯丙基烷基化反应，以非常好的产率（高达 91%）获得具有邻位季和叔立体中心的高价值 3-allyl-3-amino-2-oxindoles 和出色的对映选择性（高达 98% ee）和中等至良好的非对映选择性（高达 5:1）。进一步证明了 3-allyl-3-amino-2-oxindole 的合成效用以良好的立体选择性（dr  = 8:1 和80% ee) 通过无金属分子内碘环化反应。
• Novel O,N,N,O-tetradentate ligand from tartaric acid
  作者：Kaluvu Balaraman、Ravichandran Vasanthan、Venkitasamy Kesavan

  DOI：10.1016/j.tet.2013.05.049

  日期：2013.7

  A new class of highly stable O,N,N,O-tetradentate bioxazoline ligands were synthesized from l-tartaric acid. Exploration of those ligands in Pd-catalyzed asymmetric allylic alkylation yielded alkylated product up to 96% ee. Necessity of additional chelation to obtain high enantioselectivity was also demonstrated. Structural modifications of this ligand might result in identification of a novel privileged

  从1-酒石酸合成了一类新的高度稳定的O，N，N，O-四齿生物恶唑啉配体。在钯催化的不对称烯丙基烷基化反应中对那些配体的探索产生了烷基化产物，其ee高达96％。还证明了额外的螯合以获得高对映选择性的必要性。此配体的结构修饰可能会导致从廉价的手性库中鉴定出一种新型的优先手性配体。
• <i>C</i>₂-Symmetric Bisphosphinobioxazoline as a Chiral Ligand. Highly Enantioselective Palladium-Catalyzed Allylic Substitutions and Formation of <i>P</i>,<i>N</i>,<i>N</i>,<i>P</i> Tetradentate Palladium (II) Complexes
  作者：Sang-gi Lee、Chung Woo Lim、Choong Eui Song、Kwan Mook Kim、Chul Ho Jun

  DOI：10.1021/jo990126i

  日期：1999.6.1

  The C-2-symmetric bisphosphinobioxazoline [(S,S)-Phos-Biox] 4 was found to be a highly efficient chiral ligand for Pd-catalyzed enantioselective allylic substitution of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate and afforded enantioselectivities of up to 97% ee. Moderate enantioselectivities have been observed in Pd-catalyzed desymmetrizations of cis-1,4-bis(benzoyloxy)-cyclopent-2-ene (12) with dimethyl malonate (51-78% yield, 38-58% eel) and N-benzyl-N-methylamine (87% yield, 33% ee) nucleophiles and of biscarbamate 15 of cis-1,4-dihydroxycyclopent-2-ene (90% yield, 50% ee). A 1:1 molar mixture of(S,S)-Phos-Biox 4 with Pd(CH3CN)(2)Cl-2 and [(eta(3)-C3H5)PdCl](2) afforded the P,N,N,P-tetradentate Pd(II) complexes 19a and 19b, respectively. The structures of the complexes 19a,b were determined by X-ray analysis. The complex 19a also exhibited high enantioselectivity (86% yield, 92% ee) in allylic substitution of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate.