(-)-(S)-6-Methyl-4-chromanol | 197908-41-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: (-)-(S)-6-Methyl-4-chromanol
• 英文别名: (S)-6-methyl-4-chromanol；(S)-6-methylchroman-4-ol；(4S)-6-Methyl-3,4-dihydro-2H-1-benzopyran-4-ol；(4S)-6-methyl-3,4-dihydro-2H-chromen-4-ol
• CAS: 197908-41-1
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: IOWHBWAURDUJKJ-VIFPVBQESA-N

物化性质

• 熔点：
  83.9-84.4 °C(Solv: dichloromethane (75-09-2); hexane (110-54-3))
• 沸点：
  282.1±29.0 °C(Predicted)
• 密度：
  1.168±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  水合 6-甲基色酮 在 甲酸 、 C₃₁H₃₅ClN₂O₂RhS^(1-) 、 sodium formate 作用下， 以 水 为溶剂， 反应 3.0h， 以51%的产率得到(-)-(S)-6-Methyl-4-chromanol
  参考文献：
  名称：

  Rh(II)-Cp∗–TsDPEN catalyzed aqueous asymmetric transfer hydrogenation of chromenones into saturated alcohol: CC and CO reduction in one step

  摘要：

  As an efficient catalyst for asymmetric transfer hydrogenation reaction (ATH reaction) of alpha,beta-unsaturated ketones, Rh-Cp*-TsDPEN (Cp* = 1,2,3,4,5-pentamethylcyclopenta-1,3-diene, TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenyl- ethylenediamine) shows high chemoselectivity on C=O and C=C reduction. In our method, both C=O and C=C bonds in a variety of chromenone derivatives were reduced efficiently in aqueous media, resulting in at least 98% ee and up to 99% yields in a convenient way without further purification. The product was a useful intermediate for deriving chiral chroman-4-amine, which was reported as an effective agent against hypotension and inflammatory pain by inhibiting human bradykinin B1 receptor. (C) 2012 Published by Elsevier Ltd.

  DOI：

  10.1016/j.tetlet.2012.04.050

文献信息

• Synthesis and Reactivity of 2-Aminoethanethiolato-Bridged Dinuclear Ru(hmb) Complexes (hmb = η⁶-hexamethylbenzene): Mechanistic Consideration on Transfer Hydrogenation with Bifunctional [RuCl₂(hmb)]₂/2-Aminoethanethiol Catalyst System
  作者：Masato Ito、Akira Watanabe、Yuji Shibata、Takao Ikariya

  DOI：10.1021/om100773a

  日期：2010.10.25

  enantioselectivity for the asymmetric transfer hydrogenation of aromatic ketones using HCO2H−N(C2H5)3. In agreement with these results, the crossover experiment using a symmetrically bridged dinuclear complex, [Ru(μ-SCH2CH2NH2)(hmb)]2Cl2, and its Cp*Ir dinuclear congener, [Cp*Ir(μ-SCH2CH2NH2)]2Cl2 (Cp* = η5-C5(CH3)5), suggested that the catalytic performance in the hydrogen transfer is originated from the

  通过控制起始原料的化学计量，新制备了一系列具有桥连的2-氨基乙硫基巯基配体（S-NH）的双核Ru（hmb）配合物。它们在旋光纯仲醇的外消旋作用中的催化性能表明，除了作为活化剂的碱的量外，这些催化剂前体中Ru（hmb）和S-NH单元的相对比例对于生成环戊二烯至关重要。催化活性物质。此外，手性形式的双核Ru（S-NH）（hmb）配合物在反应性和对映选择性方面，对于使用HCO 2 H-N（C 2 H 5）3的芳族酮的不对称转移氢化反应表现出出色的催化性能。。与这些结果一致，使用对称地交叉实验桥接双核配合物，的[Ru（μ-SCH 2 CH 2 NH 2）（HMB）] 2氯2，和其的CP *铱双核同源物，混合[CP *的Ir（μ -SCH 2 CH 2 NH 2）] 2氯2（CP * =η 5 -C 5（CH 3）5），建议，在氢转移催化剂性能来源于单核酰氨复杂的Ru（SCH 2 CH 2带有Ru /
• (η⁶-Arene)Ru^II/Chiral SN Ligand: A Novel Bifunctional Catalyst System for Asymmetric Transfer Hydrogenation of Aromatic Ketones
  作者：Takao Ikariya、Masato Ito、Yuji Shibata、Akira Watanabe

  DOI：10.1055/s-0029-1217349

  日期：——

  A binary catalyst system of [RuCl2(η6-arene)]2 and a protic aminothiol (SN) ligand has been found to promote hydrogen transfer between alcohols and carbonyl compounds. The chiral catalyst system with the pipecolinol-derived chiral SN ligand displays excellent stereoselectivity in the asymmetric transfer hydrogenation of aromatic ketones using HCO2H-Et3N. Novel unsymmetrical bis(thiolate)-bridged binuclear complex, which is relevant to the generation of catalytically active species, has been synthesized and structurally characterized.

  发现了一种二元催化剂体系，由 [RuCl2(η6-芳烃)]2 和质子性氨基硫醇 (SN) 配体组成，能够促进醇和羰基化合物之间的氢转移。使用 HCO2H-Et3N 的具有哌啶醇衍生的手性 SN 配体的二元催化剂体系在对芳香酮的不对称转移氢化中显示出优异的立体选择性。合成并结构表征了一种新型非对称双硫醇盐桥连的双核配合物，该配合物与催化活性物种的生成相关。
• The Hydrogenation/Transfer Hydrogenation Network:  Asymmetric Hydrogenation of Ketones with Chiral η⁶-Arene/<i>N</i>-Tosylethylenediamine−Ruthenium(II) Catalysts
  作者：Takeshi Ohkuma、Noriyuki Utsumi、Kunihiko Tsutsumi、Kunihiko Murata、Christian Sandoval、Ryoji Noyori

  DOI：10.1021/ja0620989

  日期：2006.7.1

  Chiral eta6-arene/N-tosylethylenediamine-Ru(II) complexes, known as excellent catalysts for asymmetric transfer hydrogenation of aromatic ketones in basic 2-propanol, can be used for asymmetric hydrogenation using H2 gas. Active catalysts are generated from RuCl[(S,S)-TsNCH(C6H5)CH(C6H5)NH2](eta6-p-cymene) in methanol, but not 2-propanol, or by combination of Ru[(S,S)-TsNCH(C6H5)CH(C6H5)NH](eta6-p-cymene)

  手性 eta6-芳烃/N-甲苯磺酰乙二胺-Ru(II) 配合物被称为芳香酮在碱性 2-丙醇中不对称转移氢化的优良催化剂，可用于使用 H2 气体的不对称氢化。活性催化剂由 RuCl[(S,S)-TsNCH(C6H5)CH( )NH2](eta6-p-cymene) 在甲醇中生成，但不是 2-丙醇，或通过 Ru[(S,S) -TsNCH( )CH( )NH](eta6-p-cymene) 和 CF3SO3H 或其他非亲核酸。该方法首次实现了简单酮在酸性条件下的不对称氢化。碱敏感的 4-色满酮及其衍生物与 S,S 催化剂在甲醇中以 1000-3000 (10 atm) 至 7000 (100 atm) 的底物与催化剂摩尔比进行氢化，得到 (S)-4 -色原醇与 97% ee 定量。该反应甚至可以在 2.4 kg 的规模上实现。
• Stereochemical Sensitivity of the Human UDP-glucuronosyltransferases 2B7 and 2B17
  作者：Ingo Bichlmaier、Antti Siiskonen、Moshe Finel、Jari Yli-Kauhaluoma

  DOI：10.1021/jm051142c

  日期：2006.3.1

  A set of 28 enantiomers comprising rigid and flexible secondary alcohols was synthesized by the asymmetric Corey-Bakshi-Shibata reduction. The enantiomerically pure alcohols were subjected to enzymatic glucuronidation assays employing the human UDP-glucuronosyltransferases (UGTs) 2B7 and 2BI7. Both UGTs displayed high levels of stereo selectivity, favoring the conjugation of the (R)-enantiomers over their respective (S)-stereoisomers at eudismic ratios up to 256. The spatial arrangement of the hydroxy group determined the diastereoselectivity of the UGT2B17-catalyzed reaction in agreement with Pfeiffer's rule (eudismic activity quotient = 0.83 +/- 0.14). Inhibition studies revealed that the enantiomers had similar affinities toward the enzymes. The diastereoselectivity of the UGT-catalyzed conjugation stemmed, therefore, from the arrangement of the substrates in the catalytic site, rather than from distinct affinities toward the enzymes. Taken together, this study showed that metabolic enzymes that are generally conceived to be rather "flexible" in nature are capable of displaying high levels of chiral distinction.
• Asymmetric Hydrogenation of Aromatic Heterocyclic Ketones Catalyzed by the MsDPEN–Cp*Ir(III) Complex
  作者：Takeshi Ohkuma、Noriyuki Utsumi、Kunihiko Tsutsumi、Masahiko Watanabe、Kunihiko Murata、Noriyoshi Arai、Nobuhito Kurono

  DOI：10.3987/com-09-s(s)34

  日期：——

  Asymmetric hydrogenation of aromatic heterocyclic ketones catalyzed by Cp*Ir(OTf)(Msdpen) (MsDPEN = N-(methanesulfonyl)-1,2-diphenylethylenediamine) affords the heterocyclic alcohols in 93% to >99% ee. The reaction is conducted in a methanolic solution with a substrate-to-catalyst molar ratio of 200-5000 under 15 atm of H-2. The heterocyclic rings of substrates are left intact.