<1S,2S,5S>-2-methyl-6,8-dioxabicyclo<3,2,1>octa-4-one | 63000-65-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: <1S,2S,5S>-2-methyl-6,8-dioxabicyclo<3,2,1>octa-4-one
• 英文别名: 1,6-anhydro-3,4-dideoxy-4-C-methyl-β-D-erythro-hexopyranos-2-ulose；1,6-anhydro-3,4-dideoxy-4-C-methyl-β-D-erythro-hexopyran-2-ulose；1,6-anhydro-3,4-dideoxy-4-C-methyl-β-D-erythro-hexopyranose-2-ulose；1,6-anhydro-3,4-dideoxy-4-C-methyl-beta-D-erythrohexopyranose-2-ulose；(1S,2S,5R)-2-methyl-6,8-dioxabicyclo[3.2.1]octan-4-one
• CAS: 63000-65-7
• 化学式: C₇H₁₀O₃
• 分子量: 142.155
• InChiKey: RHCKWVDBDCBPID-UBKIQSJTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  <1S,2S,5S>-2-methyl-6,8-dioxabicyclo<3,2,1>octa-4-one 在 palladium on activated charcoal 氢氧化钾 、 正丁基锂 、 四甲基乙二胺 、 三氟化硼乙醚 、 氢气 、 4-甲基苯磺酸吡啶 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 吡啶 、 甲醇 、 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 52.0h， 生成 (3R,4R,6S)-6-(2-Ethyl-[1,3]dithian-2-yl)-4-methyl-heptan-3-ol
  参考文献：
  名称：

  左旋葡糖醛酮立体选择性合成“天然”（4S，6S，7S）-serricornin，香烟残液的性信息素

  摘要：

  Serricornin的天然立体异构体是从左旋葡糖醛酮立体选择性地合成的。这牢固地确定了Serrcornin的绝对立体化学为4S，6S，7S。还报道了（-）-δ-多striatin的短合成。

  DOI：

  10.1016/s0040-4039(00)85662-2
• 作为产物：
  描述：

  甲基锂 、 左旋葡萄糖酮 在 lithium bromide 作用下， 以 四氢呋喃 为溶剂， 反应 0.33h， 以70%的产率得到<1S,2S,5S>-2-methyl-6,8-dioxabicyclo<3,2,1>octa-4-one
  参考文献：
  名称：

  Synthetic studies on tautomycin synthesis of Segment C

  摘要：

  DOI：

  10.1016/s0040-4020(97)00229-9

文献信息

• Chiral synthons from levoglucosenone: Short routes for (—)-δ-multistriatin and (+)-prelog-djerassi lactonic acid
  作者：Masataka Mori、Tatsuji Chuman、Kunio Kato

  DOI：10.1016/0008-6215(84)85300-8

  日期：1984.7

  Abstract Levoglucosenone ( 1 ) was used as the starting material for short and stereoselective routes to chiral synthons for (—)-δ-multistriatin ( 2 ) and (+)-Prelog-Djerassi lactonic acid ( 3 ). The stereochemistry of these synthons is discussed on the basis of high-resolution 1 H-n.m.r. data.

  摘要左旋葡萄糖senone（1）被用作短和立体选择途径合成（-）-δ-multistriatin（2）和（+）-Prelog-Djerassi乳酸（3）的手性合成子的原料。这些合成子的立体化学是在高分辨率1 Hn.mr数据的基础上讨论的。
• An unusual reaction of 1,6-anhydroaldohexopyranose derivatives leading to glycals
  作者：Prakash Bhaté、Derek Horton

  DOI：10.1016/0008-6215(85)90019-9

  日期：1985.6

  Treatment of a solution of the 2-O-(N,N-dimethylsulfamoyl) derivative 3 of the levoglucosenone-derived carbocycle 1 in liquid ammonia at -40 to -50 degrees with sodium metal gave 73% of the glycal derivative 4 instead of the expected 2-deoxy derivative (2) of 1. Under the same conditions, the 2-O-(N,N-dimethylsulfamoyl) derivatives of 1,6-anhydro-3,4-dideoxy-4-C-methyl-beta-D-ribo- and -arabino-hexopyranoses

  用钠金属在液氨中以-40至-50度处理左葡萄糖葡萄糖酮衍生的碳环1的2-O-（N，N-二甲基氨磺酰基）衍生物3在液氨中的溶液，得到73％的糖基衍生物4，而不是预期的1的2-脱氧衍生物（2）。在相同条件下，1,6-脱水-3,4-二脱氧-4-C-甲基-β-的2-O-（N，N-二甲基氨磺酰基）衍生物乙酰化后，D-核糖和阿拉伯糖基六吡喃糖产生70％的6-O-乙酰基-1,5-脱水-2,3,4-三苯氧基-4-C-甲基-D-赤藓基-己糖-1 -enol。相反，从1，6-脱水-3，4-O-异亚丙基-β-D-半乳糖和-talo-吡喃糖获得的2-（N，N-二甲基-氨基磺酸盐）得到6-O-乙酰基-1。 ； 5-5-脱水-2-脱氧-3，4-O-异亚丙基-D-lyxo-hex-1-enit ol的收率很低；C-3处的氧基取代基可能会干扰导致糖基化的反应。
• Stereochemical differentiation in the reactions of organometallic reagents with levoglucosenone and some of its dihydro derivatives
  作者：I. P. Tsypysheva、F. A. Valeev、E. V. Vasil'eva、L. V. Spirikhin、G. A. Tolstikov

  DOI：10.1007/bf02495766

  日期：2000.7

  The reactions of methylmanganese iodide with levoglucosenone, its dihydro derivative, and 1.6-anhydro-3-deoxy-4-O-methyl-β-d-erythro-hexopyran-2-ulose were found to be highly diastereoselective compared to the reactions of Li-, Mg-, and Cu-based reagents. This specific feature of the manganese reagent is due to the enhanced tendency of manganese for chelation.

  与 Li 的反应相比，甲基碘化锰与左旋葡萄糖酮、其二氢衍生物和 1.6-anhydro-3-deoxy-4-O-methyl-β-d-erythro-hexopyran-2-ulose 的反应具有高度的非对映选择性-、Mg 和 Cu 基试剂。锰试剂的这一特性是由于锰螯合的趋势增强。
• 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。
• Method of preparing trans-3,4-disubstituted-.gamma.-lactones
  申请人：Japan Tobacco Inc.

  公开号：US05216177A1

  公开（公告）日：1993-06-01

  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-.beta.-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，将levoglucosenone与甲基锂在铜碘的存在下反应，以引入甲基基团到levoglucosenone的烯酮基团中，并获得1,6-脱氧-4-C-甲基-β-D-erythro-己吡喃糖-2-醛。将这种甲基化合物在醋酸中氧化生成内酯，从而得到(3S,4S)-5-羟基-3-甲基戊酸-4-内酯。进一步，将这种内酯与无水吡啶中的对甲苯磺酰氯反应，获得(3S,4S)-3-甲基-5-对甲苯磺酰氧基戊酸-4-内酯（对甲苯磺酸酯）。在铜碘的存在下，用正丙基锂烷基化获得(3S,4R)-3-甲基-4-辛内酯。这里，(3S,4S)-3-甲基-5-对甲苯磺酰氧基戊酸-4-内酯可以用碳酸钾处理一次裂解内酯环，从而获得环氧化合物。然后，用烷基化合物再次形成内酯环，获得(3S,4R)-3-甲基-4-辛内酯。