Methyl 3,4-dimethyl-2-pentenoate | 86361-91-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: Methyl 3,4-dimethyl-2-pentenoate
• 英文别名: Methyl 3,4-dimethylpent-2-enoate
• CAS: 86361-91-3
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: YDASEMNTSWHURH-UHFFFAOYSA-N

物化性质

• 沸点：
  165.4±9.0 °C(Predicted)
• 密度：
  0.900±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Methyl 3,4-dimethyl-2-pentenoate 在 platinum(IV) oxide 咪唑 、 六甲基磷酰三胺 、 lithium aluminium tetrahydride 、 四丁基氟化铵 、 氢气 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成 (20R,23R,24R)-5α-Dinosteran-29-ol
  参考文献：
  名称：

  5α-地甾烷的C-23和C-24非对映异构体的合成

  摘要：

  制备C 30生物标记物5α-地甾烷（1）的C-23和C-24非对映异构体的立体选择路线涉及（20S）-20-（碘甲基）-4α-甲基-5α-孕烯（7）与3,4-二甲基戊酸甲酯饱和酯（9）结合，然后还原，主要得到赤型-非对映异构体或7，与α，β-不饱和酯3,4-二甲基戊烯酸甲酯烷基化（12）），然后还原，主要得到苏-非对映异构体。

  DOI：

  10.1016/0040-4039(93)88018-e
• 作为产物：
  描述：

  methyl 3-hydroxy-3,4-dimethylpentanoate 在 甲醇 、 sodium 、 N,N-二甲基苯胺 作用下， 以 氯仿 为溶剂， 反应 13.0h， 生成 Methyl 3,4-dimethyl-2-pentenoate
  参考文献：
  名称：

  Hanson, James R.; O'Leary, Margaret A.; Wadsworth, Harry J., Journal of the Chemical Society. Perkin transactions I, 1983, p. 871 - 874

  摘要：

  DOI：

文献信息

• Total Syntheses of Borolithochromes A, D and G
  作者：Kanade Kirita、Hirotake Matsumoto、Gaku Endo、Seijiro Hosokawa

  DOI：10.1002/anie.202400586

  日期：2024.5.6

  Total syntheses of borolithochromes A, D and G, spiroborate natural products possessing polyaromatic ligands, were achieved by a strategy including a Diels–Alder reaction followed by a one-pot S-methylation/intramolecular Corey–Chaykovsky reaction/epoxide rearrangement. A method for the synthesis of heterocomplexes possessing different multicyclic aromatic ligands is also described.

  硼石色素 A、D 和 G（具有多芳香族配体的螺硼酸盐天然产物）的全合成通过包括 Diels-Alder 反应和一锅 S-甲基化/分子内 Corey-Chaykovsky 反应/环氧化物重排的策略实现。还描述了具有不同多环芳族配体的杂配合物的合成方法。
• Synthesis of biological markers in fossil fuels. 7. Selected diastereomers of 4.alpha.-methyl-5.alpha.-stigmastane and 5.alpha.-dinosterane
  作者：Ivan Stoilov、Ewa Kolaczkowska、David S. Watt、Jan St. Pyrek、Robert M. K. Carlson、Frederick J. Fago、J. Michael Moldowan

  DOI：10.1021/jo00064a039

  日期：1993.6

  Efficient routes for the preparation of selected C-23 and C-24 diastereomers of the C30 biological markers 4alpha-methyl-5alpha-stigmastane (1) and 5alpha-dinosterane (2) involved the alkylation of 20-(iodomethyl)-4alpha-methyl-5alpha-pregnane with either saturated or alpha,beta-unsaturated esters. The alkylation of (20S)-20-(iodomethyl)-4alpha-methyl-5alpha-pregnane with methyl (3R)-3-ethyl-4-methylpentanoate furnished methyl (20R,23zeta,24S)-4alpha-methyl-5alpha-stigmastane-23-carboxylate, and a subsequent decarbomethoxylation provided (20R,24R)-l. The alkylation of (20S)-20-(iodomethyl)-4alpha-methyl-5alpha-pregnane with methyl (3S)-3,4-dimethylpentanoate led to methyl (20R,23zeta,24R)-4alpha,24-dimethyl-5alpha-cholestane-23-carboxylate, and the reduction of this mixture provided principally (20R,23S,24R)-5alpha-dinosteran-29-ol. The further reduction of the mesylate of this isomer secured (20R,23S,24R)-5alpha-dinosterane (2a). The application of the same sequence of reactions using methyl (3R)-3,4-dimethylpentanoate led principally to (20R,23R,24S)-5alpha-dinosterane (2d). The alkylation of (20S)-20-(iodomethyl)-4alpha-methyl-5alpha-pregnane with methyl (2zeta)-3,4-dimethyl-2-pentanoate and a subsequent reduction of the ester provided a separable mixture of (20R,23R)- and (20R,23S)-5alpha-dinoster-24-(28)-en-29-ol in a 2.4:1 ratio. The conversion of (20R,23R)-5alpha-dinoster-24(28)-en-29-ol to the corresponding tert-butyldimethylsilyl ether, reduction of the DELTA24(28) bond with hydrogen over platinum oxide, and deprotection gave principally (20R,23R,24R)-5alpha-dinosteran-29-ol. The further reduction of this alcohol provided (20R,23R,24R)-5alpha-dinosterane (2b). The application of the same sequence of reactions to (20R,23S)-5alpha-dinoster-24(28)-en-29-ol provided (20R,23S,24S)-5alpha-dinosterane (2c). Diastereoselectivity at the C-23 position in these ester alkylations was examined as a function of stereochemistry at both the C-20 and C-24 positions.
• Acetolysis of (3,5,5-trimethyl-1-pyrazolin-3-yl)methyl p-bromobenzenesulfonate. Elimination of nitrogen from an azo compound via cationic intermediates
  作者：Evan L. Allred、Charles R. Flynn

  DOI：10.1021/ja00836a024

  日期：1975.2
• Synthesis of Biomarkers in Fossil Fuels: C-23 and C-24 Diastereomers of (20R)-4,17.beta.,23,24-Tetramethyl-18,19-dinorcholesta-1,3,5,7,9,11,13-heptaene
  作者：Rupa Shetty、Ivan Stoilov、David S. Watt、R. M. K. Carlson、Frederick J. Fago、J. Michael Moldowan

  DOI：10.1021/jo00105a043

  日期：1994.12

  A synthesis of the C-23 and C-24 diastereomers of triaromatic dinosteroids useful as maturation biomarkers for marine-sourced petroleum was developed. Conversion of stigmasterol to (20R,22E,24S)-4-methyl-19-norstigmasta-1,3,5(10),22-tetraene, ozonolysis of the stigmasterol sidechain, sodium borohydride reduction, and sequential treatment with methanesulfonyl chloride and sodium iodide furnished (20S)-20-(iodomethyl)-4-methyl-19-norpregna-1,3,5(10)-triene. The alkylation of this iodide with methyl 3,4-dimethyl-2-pentenoate provided the C-23R and C-23S diastereomers of methyl (20R,23 xi)-4-methyl-24-methylene-19-norcholesta-1,3,5(10)-triene-23-carboxylate, reduction with lithium aluminum hydride, and separation gave (20R,23R)- and (20R,23S)-23-(hydroxymethyl)-4-methyl-24-methylene-19-norcholesta-1,3 The further reduction of the 24-methylene and the hydroxymethyl group in (20R,23R)-23-(hydroxymethyl)-4-methyl-24-methyl-19-norcholesta-1,3,5(10)-triene provided (20R,23R,24R)- and (20R,23R,24S)-4,23,24-trimethyl-19-norcholesta-1,3,5(10)-triene. In the same fashion, the reduction of the 24-methylene and the hydroxymethyl group in (20R,23S)-23-(hydroxymethyl)-4-methyl-24-methylene-19-norcholesta-1,3, 5(10)-triene provided (20R,23S,24R)- and (20R,23S,24S)-4,23,24-trimethyl-19-norcholesta-1,3,5-(10)-triene. A chloranil oxidation of each of these monoaromatic diastereomers to (20R)-4,17 beta,23,24-tetramethyl-18,19-dinorcholesta-1,3,5,7,9,11,13,15-octaene and a catalytic hydrogenation furnished the C-23 and C-24 diastereomers of the triaromatic biomarker, (20R)-4,17 beta,23,24-tetramethyl-18,19-dinorcholesta-1,3,5,7,9,11,13-heptaene.