(3S,4S)-3-methyl-5-tosyloxypentan-4-olide | 94132-74-8

• 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: (3S,4S)-3-methyl-5-tosyloxypentan-4-olide
• 英文别名: [(2S,3S)-3-methyl-5-oxooxolan-2-yl]methyl 4-methylbenzenesulfonate
• CAS: 94132-74-8
• 化学式: C₁₃H₁₆O₅S
• 分子量: 284.333
• InChiKey: JYJJUYNIULSWPR-CMPLNLGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  78
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3S,4S)-3-methyl-5-tosyloxypentan-4-olide 在 potassium carbonate 作用下， 以 甲醇 为溶剂， 以77.7%的产率得到methyl (3S,4S)-4,5-epoxy-3-methylpentanoate
  参考文献：
  名称：

  Ebata, Takashi; Matsumoto, Katsuya; Yoshikoshi, Hajime, Heterocycles, 1993, vol. 36, # 5, p. 1017 - 1026

  摘要：

  DOI：
• 作为产物：
  描述：

  <1S,2S,5S>-2-methyl-6,8-dioxabicyclo<3,2,1>octa-4-one 在 吡啶 、 过氧乙酸 、 二甲基硫 作用下， 反应 0.5h， 生成 (3S,4S)-3-methyl-5-tosyloxypentan-4-olide
  参考文献：
  名称：

  Ebata, Takashi; Matsumoto, Katsuya; Yoshikoshi, Hajime, Heterocycles, 1993, vol. 36, # 5, p. 1017 - 1026

  摘要：

  DOI：

文献信息

• Synthesis of dolastatin G and nordolastatin G, cytotoxic 35-membered cyclodepsipeptides of marine origin
  作者：Tsuyoshi Mutou、Takashi Kondo、Takunobu Shibata、Makoto Ojika、Hideo Kigoshi、Kiyoyuki Yamada

  DOI：10.1016/0040-4039(96)01653-x

  日期：1996.9

  The synthesis of dolastatin G (1) and nordolastatin G (2), new cytotoxic cyclodepsipeptides from the Japanese sea hare Dolabella auricularia, was achieved enantioselectively, and the present result confirmed their stereostructures unambiguously.

  从日本野兔Dolabella auricularia合成新的细胞毒性环肽肽dolastatin G（1）和nordolastatin G（2），是对映选择性的，目前的结果明确证实了它们的立体结构。
• Reactions of some -ribonolactone derivatives with alkyl cuprates synthesis of (+)-eldanolide and (+)--cognac lactone
  作者：Rosa M. Ortuño、Ramon Merce、Josep Font

  DOI：10.1016/s0040-4020(01)90327-8

  日期：1987.1

  Reactions of some -ribonolactone derivatives with alkyl cuprates have been investigated in order to obtain molecules with a (4,5)-4,5-dialkyldihydro-2(3)-furanone type constitution. As a direct application, (+)-eldanolide and (+)--cognac lactone have been synthetized.

  一些的反应与烷基铜酸盐-ribonolactone衍生物以获得分子与（4被调查，5 ）-4,5- dialkyldihydro-2（3 ） -呋喃酮型的构成。作为直接的应用，已经合成了（+）-艾加醇化物和（+）-白兰地内酯。
• Novel method for converting dihydrotagetone, a bifuctional acyclic monoterpene ketone, isolated from the plant species of tagetes, into a coconut flavoured two chiral centered compound 5-isobutyl-3-methyl-4,5-dihydro-2(3H)-furanone as a novel analogue of natural whisky lactone and coconut aldehyde
  申请人：——

  公开号：US20020137949A1

  公开（公告）日：2002-09-26

  A natural inexpensive acyclic monoterpene ketone (dihydrotagetone) of formula (4), isolated from the oil of Tagetes sp., was smoothly oxidized with metaperiodate/potassium permanganate into 2,6-dimethyl-4-oxo-heptanoic acid of formula (3), the reduction of 3 with metal hydride such as sodium borohydride or lithium aluminium hydride provided 4-hydroxyacid of formula (2) which on without isolation undergone lactonisation in acidic medium furnished two chiral centered 5-isobutyl-3-methyl-4,5-dihydro-2(3H)-furanone of formula (1) as an analogue of whisky lactone 5-butyl-4-methyl-4,5-dihydro-2(3H)-furanone of formula (1a) responsible for high quality of alcoholic beverage (whisky, wine, brandy and scotch), in addition, coconut flavoured 5-butyl-4-methyl-4,5-dihydro-2(3H)-furanone of formula (1) is also as an analogue of coconut aldehyde (&ggr;-nonalactone, F.E.M.A. No. 2751) of formula (1b) which is responsible for flavouring a wide range of food stuffs including baked goods and confectionery.

  从Tagetes sp.的油中分离出的一种天然廉价无环单萜酮（二氢紫菀酮）的化学式（4），经过与高碘酸钾/高锰酸钾的平稳氧化反应，得到了化学式（3）的2,6-二甲基-4-氧代庚酸。将3还原为金属氢化物（如硼氢化钠或铝锂氢化物）可以得到化学式（2）的4-羟基酸。在酸性介质中，化学式（2）的内酯化反应未经分离，生成了两个手性中心的5-异丁基-3-甲基-4,5-二氢-2（3H）-呋喃酮，化学式为（1），作为威士忌呋喃酮5-丁基-4-甲基-4,5-二氢-2（3H）-呋喃酮的类似物，后者是高质量酒类（威士忌，葡萄酒，白兰地和苏格兰威士忌）的重要成分之一。此外，化学式（1）的椰子风味的5-丁基-4-甲基-4,5-二氢-2（3H）-呋喃酮也是椰子醛（&ggr;-壬内酯，F.E.M.A.编号2751）的类似物，后者是调味各种食品，包括糕点和糖果的重要成分之一。
• A method of preparing trans-3,4-disubstituted-gamma-lactones
  申请人：Japan Tobacco Inc.

  公开号：EP0460413A1

  公开（公告）日：1991-12-11

  First, levoglucosenone is made to react with methyl lithium in the presence of copper iodide in order to introduce a methyl group into an enone group of levoglucosenone, and to obtain 1,6-anhydro-3, 4-dideoxy-4-C-methyl-β-D-erythro-hexopyranose-2-ulose. This methyl compound is oxidized in acetic acid for lactone formation, and (3S,4S)-5-hydroxy-3-methylpentan-4-olide is thus obtained. Further, this lactone is made to react with tosyl chloride in anhydrous pyridine to obtain (3S,4S)-3-methyl-5-tosyloxypentan-4-olide (tosylate). The obtained tosylate is alkylated with n-propyl lithium in the presence of copper iodide to obtain (3S,4R)-3-methyl-4-octanolide. Here, the (3S,4S)-3-methyl-5-tosyloxypentan-4-olide may be treated with potassium carbonate to cleave lactone ring once, thereby obtaining epoxide. After that, the obtained epoxide is alkylated to form lactone ring again to obtain (3S,4R)-3-methyl-4-octanolide.

  首先，在碘化铜存在下，使左旋葡糖酮与甲基锂发生反应，从而在左旋葡糖酮的烯酮基中引入一个甲基，并得到 1,6-脱水-3,4-二脱氧-4-C-甲基-β-D-赤式吡喃糖-2-酮。这种甲基化合物在乙酸中氧化形成内酯，从而得到 (3S,4S)-5-羟基-3-甲基戊-4-内酯。再将这种内酯在无水吡啶中与对甲苯磺酰氯反应，得到 (3S,4S)-3-甲基-5-对甲苯磺酰氧基戊烷-4-内酯（对甲苯磺酸盐）。得到的对甲苯磺酸盐在碘化铜存在下与正丙基锂发生烷基化反应，得到 (3S,4R)-3-甲基-4-辛醇内酯。在这里，(3S,4S)-3-甲基-5-对甲苯磺酰氧基戊烷-4-内酯可以用碳酸钾处理，使内酯环裂解一次，从而得到环氧化物。然后，将得到的环氧化物进行烷基化，再次形成内酯环，从而得到 (3S,4R)-3-甲基-4-辛内酯。
• Ebata, Takashi; Matsumoto, Katsuya; Yoshikoshi, Hajime, Heterocycles, 1990, vol. 31, # 9, p. 1585 - 1588
  作者：Ebata, Takashi、Matsumoto, Katsuya、Yoshikoshi, Hajime、Koseki, Koshi、Kawakami, Hiroshi、Matsushita, Hajime

  DOI：——

  日期：——