1-cyclohexenylmethyl 4-methoxybenzoate | 161578-92-3

• 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: 1-cyclohexenylmethyl 4-methoxybenzoate
• 英文别名: Benzoic acid, 4-methoxy-, 1-cyclohexen-1-ylmethyl ester；cyclohexen-1-ylmethyl 4-methoxybenzoate
• CAS: 161578-92-3
• 化学式: C₁₅H₁₈O₃
• 分子量: 246.306
• InChiKey: YTOADMMHYFXNEF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-cyclohexenylmethyl 4-methoxybenzoate 在 potassium hexacyanoferrate(III) potassium osmate(VI) 、 (R)-proline based C₃₇H₄₂N₆O₃ 、 potassium carbonate 作用下， 以 水 、 叔丁醇 为溶剂， 反应 24.0h， 以95%的产率得到(1R,2R)-1-(((4-methoxybenzoyl)oxy)methyl)-1,2-cyclohexanediol
  参考文献：
  名称：

  机械指导的设计导致了用于烯烃的高对映选择性，催化二羟基化的有效和实用的新试剂的合成。

  摘要：

  [结构：见正文]使用脯氨酸基催化剂以高对映选择性完成了烯烃的催化不对称二羟基化反应。显示了苯乙烯的过渡前态组装体。

  DOI：

  10.1021/ol035192s
• 作为产物：
  描述：

  3-甲氧基环己烯 、 对甲氧基苯甲酰氯 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以95%的产率得到1-cyclohexenylmethyl 4-methoxybenzoate
  参考文献：
  名称：

  The application of a mechanistic model leads to the extension of the Sharpless asymmetric dihydroxylation to allylic 4-methoxybenzoates and conformationally related amine and homoallylic alcohol derivatives.

  摘要：

  The scope and utility of the Sharpless asymmetric dihydroxylation has been expanded to include the use of allylic 4-methoxybenzoates as precursors of a wide variety of substituted chiral glycerol derivatives. The allylic 4-methoxybenzoyl group was found to be superior to other allylic alcohol protecting groups with respect to both yield and enantiomeric purity of the product. For example, asymmetric dihydroxylation of allyl 4-methoxybenzoate (6a) using the (DHQD)(2)PYDZ . OsO4 (1 . OsO4) catalyst system affords (S)-3-(4-methoxybenzoyloxy)-1,2-propanediol (7a) in >99% yield and 98% ee. The 4-methoxybenzoates of a variety of other allylic alcohols also serve as excellent substrates, in contrast to the parent alcohols themselves. The efficient asymmetric dihydroxylation of homoallylic 4-methoxyphenyl ethers (12a and 15), allyl 9-fluorenimine (18b), bis(homoallyl) 4-methoxybenzoate (14) and other structurally related substrates is also described. This methodology was developed under mechanistic guidance from the transition state model advanced earlier by us for the bis-cinchona alkaloid catalyzed asymmetric dihydroxylation reaction. The 4-methoxybenzoyl group functions not only to selectively protect one of the hydroxy groups of the product triol for subsequent synthetic manipulation but also to provide an extended binding group that participates in hydrophobic and aryl-aryl interactions with the U-shaped binding pocket of the (DHQD)(2)PYDZ . OsO4 catalyst (1 . OsO4), thereby enhancing enantioselectivity.

  DOI：

  10.1021/ja00149a003

文献信息

• Kinetic Resolution by Enantioselective Dihydroxylation of Secondary Allylic 4-Methoxybenzoate Esters Using a Mechanistically Designed Cinchona Alkaloid Catalyst
  作者：E. J. Corey、Mark C. Noe、Angel Guzman-Perez

  DOI：10.1021/ja00149a004

  日期：1995.11

  The OsO4-cinchona alkaloid catalyzed asymmetric dihydroxylation process has been applied successfully to the kinetic resolution of 1-substituted allylic alcohols by the use of the 4-methoxybenzoyl derivatives in conjunction with the specifically designed DHQD-PYDZ(S)-anthryl catalyst (5 . OsO4). Thus, (+/-)-3-buten-2-yl 4-methoxybenzoate (4a) and (+/-)-1-phenyl-2-propen-1-yl 4-methoxybenzoate (4b) have been kinetically resolved with relative rate constants of 20 and 79, respectively. These values are among the best reported for the kinetic resolution of racemic compounds using non-enzymatic catalyst systems. The design of this resolution process was accomplished under mechanistic guidance using the transition state model proposed recently for the asymmetric dihydroxylation process. The specially selected ligand 5 possesses a deep U-shaped binding pocket with both the methoxyquinoline and the 1-anthryl walls projecting rearward of the pyridazine linker group at the floor. This catalyst not only recognizes the 4-methoxybenzoyl group of these substrates, which extends into the distant binding pocket of the catalyst, but also provides an open space adjacent to one of the allylic alpha-substituents of the substrate which allows for enantiomeric selection in the dihydroxylation. The magnitude of the kinetic resolution and the absolute stereopreference for the dihydroxylation reaction provide strong evidence for the guiding mechanistic model. The utility of this process is clearly demonstrated by the selective dihydroxylation of 1,4-pentadien-3-yl 4-methoxybenzoate (10) to give diol 11 in 70% isolated yield with >98% ee and >96% de.
• Short Enantioselective Synthesis of (-)-Ovalicin, a Potent Inhibitor of Angiogenesis, Using Substrate-Enhanced Catalytic Asymmetric Dihydroxylation
  作者：E. J. Corey、Angel Guzman-Perez、Mark C. Noe

  DOI：10.1021/ja00105a084

  日期：1994.12
• 4, 5-DIARYLOXAZOLE COMPOUNDS
  申请人：FUJISAWA PHARMACEUTICAL CO., LTD.

  公开号：EP1027340A1

  公开（公告）日：2000-08-16
• US6297267B1
  申请人：——

  公开号：US6297267B1

  公开（公告）日：2001-10-02
• [EN] 4, 5-DIARYLOXAZOLE COMPOUNDS<br/>[FR] COMPOSES DE 4,5-DIARYLOXAZOLE
  申请人：FUJISAWA PHARMACEUTICAL CO., LTD.

  公开号：WO1999021843A1

  公开（公告）日：1999-05-06

  (EN) Compounds of formula (I) wherein R1 is hydrogen or carboxy protective group, R2, R5, R6 and R7 are each hydrogen or hydroxy, R3 and R4 are each hydrogen, or combined to form epoxy or single bond, R8 and R9 are each optionally substituted aryl, and X is single bond or methylene, in addition to the above, R2 and R3 may be combined to form single bond; provided that when R2, R5, R6 and R7 are each hydrogen, then R3 and R4 are combined to form epoxy; when R3 and R4 are combined to form single bond, then at least one of R2, R5, R6 and R7 is hydroxy and the other(s) is (are) hydrogen; and when R3 and R4 are each hydrogen, then at least one of R2, R5, R6 and R7 is hydroxy and the other(s) is (are) hydrogen, and X is methylene, or its salt, process for preparing it, a pharmaceutical composition including it, and a use thereof.(FR) La présente invention porte sur des composés de la formule (I), dans laquelle R1 est hydrogène ou un groupe protecteur carboxylique, R2, R5 et R7 sont chacun hydrogène ou hydroxy, R3 et R4 sont chacun hydrogène, ou combinés pour former un époxy ou une liaison simple, R8 et R9 sont chacun à titre facultatif aryle substitué, et X est une liaison simple ou méthylène. En plus de ce qui précède, R2 et R3 peuvent être combinés pour former une liaison simple, à condition que, lorsque R2, R5, R6 et R7 sont chacun hydrogène, R3 et R4 soient combinés pour former un époxy; que, lorsque R3 et R4 sont combinés pour former une liaison simple, au moins un élément parmi R2, R5, R6 et R7 soit hydroxy et que l'autre ou les autres soi(en)t hydrogène; et que, lorsque R3 et R4 sont chacun hydrogène, au moins un élément parmi R2, R5, R6 et R7 soit hydroxy, que l'autre ou les autres soi(en)t hydrogène et que X soit méthylène. L'invention porte également sur les sels desdits composés, sur le mode de préparation, sur une composition pharmaceutique contenant un tel composé, et sur une application.