methyl (4R,5S)-4,5-dihydroxyhex-2E-enoate | 63357-08-4

• 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 (4R,5S)-4,5-dihydroxyhex-2E-enoate
• 英文别名: methyl (E,4R,5S)-4,5-dihydroxy-2-hexenoate；methyl (E,4R,5S)-4,5-dihydroxyhex-2-enoate
• CAS: 63357-08-4
• 化学式: C₇H₁₂O₄
• 分子量: 160.17
• InChiKey: JEDCCDABYXNUDA-NBZFHMRBSA-N

物化性质

• 沸点：
  297.3±40.0 °C(Predicted)
• 密度：
  1.169±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (4R,5S)-4,5-dihydroxyhex-2E-enoate 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 sodium hydroxide 、 sodium tetrahydroborate 、 三丁基膦 、 2,4,6-三氯苯甲酰氯 、 D(+)-10-樟脑磺酸 、 水 、 sodium acetate 、 溶剂黄146 、 三乙胺 、 N,N'-二环己基碳二亚胺 、 锌 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 60.5h， 生成
  参考文献：
  名称：

  New total syntheses of (+)-macrosphelides C, F and G

  摘要：

  The total synthesis of (+)-macrosphelide C 1 (25% overall yield in nine steps), (+)-macrosphelide F 2 (20% overall yield in nine steps) and (+)-macrosphelide G 3 (22% overall yield in nine steps) has been achieved from the chemoenzymatic reaction product (4R,5S)-4-benyloxy-5-hydroxy-(2E)-hexenoate 7. (C) 2002 Published by Flsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(02)00180-5
• 作为产物：
  描述：

  methyl (4R,5S)-4-benzyloxy-5-hydroxy-2(E)-hexenoate 在 三氯化铝 作用下， 以 二氯甲烷 、 xylene 为溶剂， 反应 0.5h， 以78%的产率得到methyl (4R,5S)-4,5-dihydroxyhex-2E-enoate
  参考文献：
  名称：

  由非手性前体，山梨酸甲酯化学合成N-三氟乙酰基-1-牛磺胺，N-三氟乙酰基-1-香豆胺，N-苯甲酰基-d-花生胺和N-苯甲酰基-d-香豆胺

  摘要：

  将苄基胺共轭加成到甲基（4 R，5 S）-4,5-（异丙基二烯二氧基）-（2 E）-己酸8a中，然后在酸性条件下内酯化，可以完成l-柔红胺4和l-的正式合成。二十胺2。另一方面，将苄胺直接共轭加成到（4 S，5 S）-4,5-环氧-（2 E）-己酸甲酯5上，随后分子内的亲核攻击被环氧基环上的酯羰基攻击底物导致d-花生胺2和d-ristosamine 1的正式全部合成。

  DOI：

  10.1016/s0957-4166(00)00395-5

文献信息

• Novel antitumour metabolites produced by a fungal strain from a sea hare
  作者：Atsushi Numata、Masashi Iritani、Takeshi Yamada、Katsuhiko Minoura、Eiko Matsumura、Takao Yamori、Takashi Tsuruo

  DOI：10.1016/s0040-4039(97)10198-8

  日期：1997.11

  Pericosines A (1) and B (2), and macrosphelides E - H (3 – 6) have been isolated, along with known macrosphelide C (7), from a strain of Periconia byssoides originally separated from the sea hare Aplysia kurodai, and their structures have been established on the basis of spectral analyses. Compounds 1 and 2 exhibited significant inhibitory activity in vitro against tumour cells, and the former also

  Pericosines A（1）和B（2），和macrosphelidesë - H（3 - 6）已被分离，用公知的macrosphelide C（沿7），从菌株Periconia byssoides最初从海兔分离海兔kurodai，和它们的结构是在光谱分析的基础上建立的。化合物1和2在体外对肿瘤细胞表现出显着的抑制活性，并且前者在体内也表现出显着的体内肿瘤抑制活性。
• Absolute stereostructures of cell-adhesion inhibitors, macrosphelides C, E–G and I, produced by a Periconia species separated from an Aplysia sea hare
  作者：Takeshi Yamada、Masashi Iritani、Mitsunobu Doi、Katsuhiko Minoura、Tadayoshi Ito、Atsushi Numata

  DOI：10.1039/b104337b

  日期：2001.11.15

  Macrosphelides E–I have been isolated, along with known macrosphelides A and C, from a strain of Periconia byssoides originally separated from the sea hare Aplysia kurodai, and the absolute stereostructures of macrosphelides E–G and I have been elucidated on the basis of spectroscopic analyses using 1D and 2D NMR techniques and some chemical transformations. In addition, the absolute configuration of macrosphelide C, previously undetermined, has been established by X-ray analysis and application of the modified Mosher method. Macrosphelides E–H inhibited the adhesion of human-leukaemia HL-60 cells to HUVEC.

  宏球苷E–I与已知的宏球苷A和C一起从最初从海兔Aplysia kurodai分离出的Periconia byssoides菌株中提取出来，并且宏球苷E–G和I的绝对立体结构已通过使用1D和2D NMR技术的光谱分析及一些化学转化进行阐明。此外，之前未确定的宏球苷C的绝对构型已通过X射线分析和改良的Mosher方法确立。宏球苷E–H抑制了人类白血病HL-60细胞与HUVEC的粘附。
• Cordybislactone, a stereoisomer of the 14-membered bislactone clonostachydiol, from the hopper pathogenic fungus Cordyceps sp. BCC 49294: revision of the absolute configuration of clonostachydiol
  作者：Ken-ichi Ojima、Arunrat Yangchum、Pattiyaa Laksanacharoen、Kanoksri Tasanathai、Donnaya Thanakitpipattana、Hidetoshi Tokuyama、Masahiko Isaka

  DOI：10.1038/s41429-017-0008-9

  日期：2018.3

  Cordybislactone (3), a new stereoisomer of the 14-membered bislactone clonostachydiol, together with its open ring analog (4), was isolated from the hopper pathogenic fungus Cordyceps sp. BCC 49294. The relative and absolute configurations of 3 were determined by chemical derivatizations, including the modified Mosher’s method. The stereochemistry of clonostachydiol was determined using the natural compound isolated from Xylaria sp. BCC 4297. The result revealed that the absolute configuration of clonostachydiol, previously determined by synthesis, should be revised to its enantiomer.

  Cordybislactone (3)是一种新的14元双内酯克隆石蜡醇的立体异构体，以及其开放环类似物（4），从跳虫病原真菌Cordyceps sp. BCC 49294中分离出来。通过化学衍生反应，包括改进的Mosher法，确定了3的相对和绝对构型。克隆石蜡醇的立体化学是通过从Xylaria sp. BCC 4297中分离的天然化合物来确定的。结果表明，之前通过合成确定的克隆石蜡醇的绝对构型应修正为其对映体。
• Synthesis of γ- and δ-Lactone Natural Products by Employing a trans–cis Isomerization/Lactonization Strategy
  作者：Machiko Ono、Keisuke Kato、Hiroyuki Akita

  DOI：10.1248/cpb.c12-01026

  日期：——

  Alkaline hydrolysis of 4-hydroxy- or/and 5-hydroxy-(2E)-alkenoate followed by acid treatment gave the corresponding (2E)-alkenoic acids which were subjected to lactone formation reaction without further purification. The crude acids were treated with 2,4,6-trichlorobenzoyl chloride in pyridine to afford γ-lactone or δ-lactone, respectively, accompanied by trans–cis isomerization. By this procedure, (±)-(4,5)-trans-5-benzyloxy-2-hexen-4-olide (90% overall yield), (S)-5-hydroxy-2-penten-4-olide (86% overall yield), (4S,5R)-5-hydroxy-2-hexen-4-olide (86% overall yield), (4R,5S)-5-hydroxy-2-hexen-4-olide (82% overall yield), (S)-parasorbic acid (58% overall yield) and natural product, (5R,7S)-7-hydroxy-2-octen-5-olide (euscapholide: 20% overall yield) were synthesized.

  4-羟基或/和5-羟基-(2E)-烯酸盐的碱性水解后进行酸处理，得到了相应的(2E)-烯酸，然后未经过进一步纯化直接进行内酯形成反应。粗酸与2,4,6-三氯苯甲酰氯在吡啶中反应，分别生成γ-内酯或δ-内酯，并伴随有反-顺异构化。通过这种方法合成了(±)-(4,5)-反-5-苄氧基-2-己烯-4-内酯（整体产率90%）、(S)-5-羟基-2-戊烯-4-内酯（整体产率86%）、(4S,5R)-5-羟基-2-己烯-4-内酯（整体产率86%）、(4R,5S)-5-羟基-2-己烯-4-内酯（整体产率82%）、(S)-伐索酸（整体产率58%）以及天然产物(5R,7S)-7-羟基-2-辛烯-5-内酯（优蔬内酯：整体产率20%）。
• Ono, Machiko; Saotome, Chikako; Akita, Hiroyuki, Heterocycles, 1997, vol. 45, # 7, p. 1257 - 1261
  作者：Ono, Machiko、Saotome, Chikako、Akita, Hiroyuki

  DOI：——

  日期：——