3-methyl-2-butenyl methanesulfonate | 59867-97-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 3-methyl-2-butenyl methanesulfonate
• 英文别名: prenyl mesylate；3-Methyl-2-buten-1-yl-methansulfonat；3-Methylbut-2-enyl methanesulfonate
• CAS: 59867-97-9
• 化学式: C₆H₁₂O₃S
• 分子量: 164.225
• InChiKey: XUKWPBWUNQFYIW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-methyl-2-butenyl methanesulfonate 在 2,6-二甲基吡啶 、 水 作用下， 以 丙酮 为溶剂， 生成 异戊烯醇
  参考文献：
  名称：

  Dimethylallyltryptophan synthase. An enzyme-catalyzed electrophilic aromatic substitution

  摘要：

  Dimethylallyltryptophan (DMAT) synthase catalyzes the alkylation of L-tryptophan at C(4) by dimethylallyl diphosphate (DMAPP) in the first pathway-specific step in the biosynthesis of ergot alkaloids. The mechanism of the reaction was studied with analogs of both substrates. Five 7-substituted derivatives of N-acetyltryptophan (2, Z = OCH3, CH3, F, CF3, and NO2) were synthesized. The L enantiomers of the free amino acids were obtained by selective hydrolysis of the racemate using aminoacylase from Aspergillus. In addition, the E and Z fluoromethyl and difluoromethyl analogs of DMAPP (1, Y = CH3, CH2F, CHF2) were prepared. Rates of the enzyme-catalyzed reactions were measured for the dimethylallyl derivatives with L-tryptophan and for the L-tryptophan derivatives with DMAPP. In addition, the relative reactivities of the methanesulfonate derivatives of the DMAPP analogs were determined for solvolysis in aqueous acetone. A Hammett plot for the tryptophan analogs gave a good linear correlation with rho = -2.0. In addition, a Hammett plot of the logarithms of the relative rates of solvolysis and enzyme-catalyzed alkylation gave a positive linear correlation. These results indicate that the prenyl-transfer reaction catalyzed by DMAT synthase is an electrophilic aromatic substitution and is mechanistically similar to the electrophilic alkylation catalyzed by farnesyl diphosphate synthase.

  DOI：

  10.1021/ja00045a004
• 作为产物：
  描述：

  isopentenyl methyl prenyl sulfonium methane sulfonate 在 N,N-二异丙基乙胺 作用下， 生成 3-methyl-2-butenyl methanesulfonate
  参考文献：
  名称：

  C-prenylation of isopentenyl derivatives with sulfonium salts

  摘要：

  DOI：

  10.1016/s0040-4039(00)98366-7

文献信息

• Enantioselective Claisen Rearrangements with a Hydrogen-Bond Donor Catalyst
  作者：Christopher Uyeda、Eric N. Jacobsen

  DOI：10.1021/ja803370x

  日期：2008.7.1

  m ion associated with the noncoordinating BArF counterion is shown to be an effective catalyst for the [3,3]-sigmatropic rearrangement of a variety of substituted allyl vinyl ethers. Highly enantioselective catalytic Claisen rearrangements of ester-substituted allyl vinyl ethers are then documented using a new C2-symmetric guanidinium ion derivative.

  与非配位 BArF 反离子相关的 N,N'-二苯基胍离子被证明是各种取代烯丙基乙烯基醚 [3,3]-σ 重排的有效催化剂。然后使用新的 C2 对称胍离子衍生物记录了酯取代的烯丙基乙烯基醚的高度对映选择性催化克莱森重排。
• Catalytic Enantioselective Claisen Rearrangements of O-Allyl β-Ketoesters
  作者：Christopher Uyeda、Andreas R. Rötheli、Eric N. Jacobsen

  DOI：10.1002/anie.201005183

  日期：2010.12.10

  A chiral guanidinium ion is shown to catalyze enantioselective Claisen rearrangements of O‐allyl β‐ketoesters in 78–87 % ee (see scheme). The pericyclic nature of the process allows products containing vicinal stereogenic centers to be accessed with both enantio‐ and diastereocontrol.

  手性胍离子在 78-87% ee 中催化O-烯丙基 β-酮酯的对映选择性克莱森重排（见方案）。该过程的周环性质允许通过对映和非对映控制访问含有邻位立体中心的产品。
• METHOD FOR PRODUCING ALKYL 5-METHYL-5-HEXENOATE
  申请人：Ujita Katsuji

  公开号：US20120253062A1

  公开（公告）日：2012-10-04

  A decarboxylation reaction of a (3-methyl-3-butenyl)malonic acid dialkyl ester, carried out by heating in the presence of water and a base, produces an alkyl 5-methyl-5-hexenoate. The decarboxylation reaction produces the alkyl 5-methyl-5-hexenoate inexpensively and effectively. The base can optionally be a tertiary amine compound or a heterocyclic amine compound. Producing the alkyl 5-methyl-5-hexenoate can optionally further include removing an alcohol.

  (3-甲基-3-丁烯基)丙二酸二烷基酯的脱羧反应，在水和碱的存在下加热进行，产生烷基5-甲基-5-己烯酸酯。脱羧反应以廉价且有效的方式产生烷基5-甲基-5-己烯酸酯。碱可以选择性地是三级胺化合物或杂环胺化合物。生产烷基5-甲基-5-己烯酸酯还可以选择性地包括去除醇。
• Carboxylic acid derivatives useful for inhibiting the degradation of cartilage
  申请人：PFIZER INC.

  公开号：EP0130795A2

  公开（公告）日：1985-01-09

  Certain carboxylic acids of the formula and the pharmaceutically-acceptable salts thereof, and certain esters and amides thereof, are useful for inhibiting the degradation of articular cartilage when administered to a mammalian subject afflicted with an arthritic disease. X is O, S,SO, S02, NH, NCH3 or NCOCH3; R1 is H or CH3; and n is zero or one.

  某些式羧酸 及其药学上可接受的盐，以及它们的某些酯和酰胺，在给患有关节炎疾病的哺乳动物施用时，可用于抑制关节软骨的降解。X 是 O、S、SO、S02、NH、N 或 NCO ；R1 是 H 或 CH3；n 是 0 或 1。
• PROCESS FOR PREPARATION OF ALKYL 5-METHYL-5-HEXENOATES
  申请人：Kuraray Co., Ltd.

  公开号：EP2514738A1

  公开（公告）日：2012-10-24

  A method capable of industrially inexpensively and effectively producing an alkyl 5-methyl-5-hexenoate is provided. The present invention is a method for producing an alkyl 5-methyl-5-hexenoate, comprising a decarboxylation reaction of a (3-methyl-3-butenyl)malonic acid dialkyl ester carried out by heating in the presence of water and a base.

  本发明提供了一种能够在工业上廉价而有效地生产 5-甲基-5-己烯酸烷基酯的方法。 本发明是一种生产 5-甲基-5-己烯酸烷基酯的方法，包括在水和碱存在下，通过加热对（3-甲基-3-丁烯基）丙二酸二烷基酯进行脱羧反应。