(R)-(3-methoxyphenyl)(phenyl)methanol

• 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: (R)-(3-methoxyphenyl)(phenyl)methanol
• 英文别名: (R)-(3-methoxyphenyl)-phenylmethanol
• 化学式: C₁₄H₁₄O₂
• 分子量: 214.264
• InChiKey: TWFPWTCZBHLWHQ-CQSZACIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-(3-methoxyphenyl)(phenyl)methanol 在 (1R,aR)-3-二苯基膦基-2-(4-二苯基膦基-2,5-二甲基-3-噻吩基)-1,7,7-三甲基-双环[2.2.1]庚-2-烯 、 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 作用下， 以 四氢呋喃 为溶剂， 反应 14.0h， 生成
  参考文献：
  名称：

  芳烃 C-H 键的铑催化对映选择性硅烷化：二芳基甲醇的去对称化

  摘要：

  我们报告了由（氢化）甲硅烷基引导的芳烃 CH 键的 Rh 催化、对映选择性甲硅烷基化。在 [Rh(cod)Cl]2 和手性双膦配体存在下，通过二苯甲酮或其衍生物的氢化硅烷化原位形成的（氢化）甲硅烷基醚以高产率进行不对称 CH 甲硅烷基化，具有优异的对映选择性。该过程的立体选择性还允许对映体富集的二芳基甲醇以一个芳基相对于另一个芳基的位点选择性反应。来自甲硅烷基化过程的对映体富集的苯并恶唑经过一系列转变，形成 CC、CO、Cl 或 C-Br 键。

  DOI：

  10.1021/jacs.5b03091
• 作为产物：
  描述：

  2-(dimethyl(phenyl)silyl)-5-methoxybenzaldehyde 在 bis(1,5-cyclooctadiene)nickel (0) 、 四丁基氟化铵 、 sodium t-butanolate 、 (4R,5R)-1,3-bis-(2-isopropylphenyl)-4,5-diphenyl-4,5-dihydro-3H-imidazol-1-ium tetrafluoroborate 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 9.0h， 生成 (R)-(3-methoxyphenyl)(phenyl)methanol
  参考文献：
  名称：

  Nickel(0)-Catalyzed Enantio- and Diastereoselective Synthesis of Benzoxasiloles: Ligand-Controlled Switching from Inter- to Intramolecular Aryl-Transfer Process

  摘要：

  A highly enantioselective synthesis of 3-aryl-, vinyl-, and alkynyl-2,1-benzoxasiloles (up to 99.9% ee and 99% yield) was achieved via the sequential activation of an aldehyde and a silane by nickel(0). This strategy was applied to a simultaneous generation of carbon- and silicon-stereogenic centers with excellent selectivity (dr = 99:1) via diastereotopic aryl transfer. Initial mechanistic studies revealed the complete switching of an aryl-transfer process from an intermolecular (racemic synthesis in the presence of IPr) to an intramolecular (enantioselective synthesis using chiral NHC, L5) fashion. A plausible rationale for the switching of the aryl-transfer process is given by a preliminary DFT calculation, which suggests that the coordination of 1 to the nickel(0)/L5 fragment in an eta(2)-arene:eta(2)-aldehyde fashion would be a key to the intramolecular process, while the formation of the corresponding intermediate is not possible in the presence of IPr. Owing to the chemically labile nature of its C-Si and O-Si bonds, enantioenriched benzoxasiloles are utilized for the synthesis of chiral building blocks and antihistaminic and anticholinergic drug molecules such as (R)-orphenadrine and (S)-neobenodine with no erosion of the enantiomeric excess.

  DOI：

  10.1021/jacs.5b07827

文献信息

• Highly Enantioselective Addition of In Situ Prepared Arylzinc to Aldehydes Catalyzed by a Series of Atropisomeric Binaphthyl-Derived Amino Alcohols
  作者：Gui Lu、Fuk Yee Kwong、Ji-Wu Ruan、Yue-Ming Li、Albert S. C. Chan

  DOI：10.1002/chem.200501048

  日期：2006.5.15

  catalyst, both enantiomers of many pharmaceutically interesting diarylmethanols can be obtained by the proper combination of various arylzinc reagents with different aldehydes; this catalytic system also works well for the phenylation of aliphatic aldehydes to give up to 96 % ee.

  用手性联萘衍生的氨基醇作为催化剂直接将原位制备的芳基锌加到醛中可以提供高收率和优异的对映选择性（高达99％ee，ee =对映体过量）的旋光二芳基甲醇。通过使用单一催化剂，可以通过将各种芳基锌试剂与不同的醛适当组合来获得许多可药用的二芳基甲醇的两种对映异构体。该催化体系也可以很好地用于脂族醛的苯基化反应，以产生高达96％的ee。
• A Chiral Ruthenium-Monophosphine Catalyst for Asymmetric Addition of Arylboronic Acids to Aryl Aldehydes
  作者：Ke Li、Naifu Hu、Renshi Luo、Weicheng Yuan、Wenjun Tang

  DOI：10.1021/jo400850m

  日期：2013.6.21

  A novel ruthenium catalyst on the basis of a chiral monophosphorus ligand is efficient for the asymmetric addition of arylboronic acids to aryl aldehydes, providing a series of chiral diarylmethanols in excellent yields and enantioselectivities (up to 92% ee). Preliminary study has shown that this process is catalyzed by a Ru complex with a single monophosphorus ligand.

  基于手性单磷配体的新型钌催化剂可有效地将芳基硼酸不对称加成到芳基醛上，从而以优异的收率和对映选择性（高达92％ee）提供一系列手性二芳基甲醇。初步研究表明，此过程是由具有单个单磷配体的Ru络合物催化的。
• Application of a Heterogeneous Chiral Titanium Catalyst Derived from Silica-Supported 3-Aryl H₈-BINOL to Enantioselective Alkylation and Arylation of Aldehydes
  作者：Junichiro Akai、Satoshi Watanabe、Kumiko Michikawa、Toshiro Harada

  DOI：10.1021/acs.orglett.7b01625

  日期：2017.7.7

  derivative as a precursor, and the resulting silica-supported ligand (6 mol %) was employed in the enantioselective alkylation and arylation of aldehydes in the presence of Ti(OiPr)4. The reactions using Et2Zn, Et3B, and aryl Grignard reagents all afforded the corresponding adducts in high enantioselectivities and yields. The silica-immobilized titanium catalyst could be reused up to 14 times without appreciable

  使用氢硅烷衍生物作为前体，将3-芳基H 8 -BINOL接枝到硅胶表面，并将所得的二氧化硅负载的配体（6 mol％）用于在乙腈存在下的醛的对映选择性烷基化和芳基化。 Ti（O i Pr）4。使用Et 2 Zn，Et 3 B和芳基格氏试剂的反应均以高对映选择性和收率提供了相应的加合物。二氧化硅固定的钛催化剂可以重复使用多达14次，而不会明显降低活性。
• Substituent Position‐Controlled Stereoselectivity in Enzymatic Reduction of Diaryl‐ and Aryl(heteroaryl)methanones
  作者：Zhining Li、Zexu Wang、Yuhan Wang、Xiaofan Wu、Hong Lu、Zedu Huang、Fener Chen

  DOI：10.1002/adsc.201801543

  日期：2019.4.16

  directing group (bromo group) showcased the potential application of this substrate‐controlled bioreduction reaction. The combined use of substrate engineering and protein engineering, was demonstrated to be a useful strategy in efficiently improving stereoselectivity or switching stereopreference of enzymatic processes.

  我们在这里报告了一种名为KmCR2的新型酮还原酶（KRED）的发现，该酮具有对大体积的二芳基和芳基（杂芳基）甲烷进行生物还原的广泛的底物光谱。芳环上取代基的位置（间位与对位或邻位被揭示出可以控制KmCR2的立体特异性。使用经过精心设计的带有无痕导向基团（溴基）的底物，对二芳基或芳基（杂芳基）甲醇的两种对映异构体进行立体选择性制备，证明了这种底物控制的生物还原反应的潜在应用。底物工程和蛋白质工程的结合使用被证明是有效提高立体选择性或切换酶促过程的立体偏好的有用策略。
• Remarkably Efficient Enantioselective Titanium(IV)−(<i>R</i>)-H₈-BINOLate Catalyst for Arylations to Aldehydes by Triaryl(tetrahydrofuran)aluminum Reagents
  作者：Kuo-Hui Wu、Han-Mou Gau

  DOI：10.1021/ja062080y

  日期：2006.11.1

  Novel asymmetric triarylaluminum AlAr3(THF) additions to aldehydes catalyzed by 10 mol % of the titanium(IV) complex of (R)-H8-BINOL ligand are reported. The catalytic system is extremely efficient with reactions completing within 10 min. The system applies to the most diversified aldehydes to date, and more than 20 aldehydes were examined to afford diarylmethanols having an electron-donating or an

  报道了由 (R)-H8-BINOL 配体的钛 (IV) 配合物的 10 mol% 催化的新型不对称三芳基铝 AlAr3(THF) 加成反应。催化系统非常高效，反应在 10 分钟内完成。该系统适用于迄今为止最多样化的醛，并检查了 20 多种醛，以提供在芳基部分的 2-、3-或 4-位具有给电子或吸电子基团的二芳基甲醇，线性或支链 1-芳基脂肪醇、芳基呋喃基甲醇、1-芳基烯丙醇，尤其是 1-芳基炔丙醇，具有 >/=90% ee 的优异对映选择性，但 1-萘基加成到苯甲醛的情况除外。值得注意的是，可以获得 R-和 S-构型的二芳基甲醇。