(1aR-(1aalpha,6beta,7alpha,7aalpha,7balpha))-4,5,6,7,7a,7b-六氢-6-羟基-1a-(1-(羟基甲基)乙烯基)-7,7a-二甲基-萘并(1,2-b)环氧乙烯-2(1aH)-酮 | 55785-58-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: (1aR-(1aalpha,6beta,7alpha,7aalpha,7balpha))-4,5,6,7,7a,7b-六氢-6-羟基-1a-(1-(羟基甲基)乙烯基)-7,7a-二甲基-萘并(1,2-b)环氧乙烯-2(1aH)-酮
• 英文名称: (3R,4R,5R,6R,7R)-phomenone
• 英文别名: (+)-phomenone；phomenone；Phomenon；(1aR,6R,7R,7aR,7bR)-6-hydroxy-1a-(3-hydroxyprop-1-en-2-yl)-7,7a-dimethyl-5,6,7,7b-tetrahydro-4H-naphtho[1,2-b]oxiren-2-one
• CAS: 55785-58-5
• 化学式: C₁₅H₂₀O₄
• 分子量: 264.321
• InChiKey: WKZMDQXEUJZALS-OANMRLRGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  70.1
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1aR-(1aalpha,6beta,7alpha,7aalpha,7balpha))-4,5,6,7,7a,7b-六氢-6-羟基-1a-(1-(羟基甲基)乙烯基)-7,7a-二甲基-萘并(1,2-b)环氧乙烯-2(1aH)-酮 在 manganese(IV) oxide 作用下， 生成 13-Aldophomenone
  参考文献：
  名称：

  Sugawara, Fumio; Hallock, Yali F.; Bunkers, Greg D., Bioscience, Biotechnology and Biochemistry, 1993, vol. 57, # 2, p. 236 - 239

  摘要：

  DOI：
• 作为产物：
  描述：

  (3S,4R,4aR,5R,6R)-6-t-butyldimethylsilyloxy-3,4-epoxy-3-isopropenyl-4a,5-dimethyl-4,4a,5,6,7,8-hexahydro-2(3H)-naphthalenone 在 吡啶 、 氢氟酸 、 phenylselenenyl trifluoroacetate 、 间氯过氧苯甲酸 作用下， 以 乙腈 为溶剂， 反应 5.33h， 生成 (1aR-(1aalpha,6beta,7alpha,7aalpha,7balpha))-4,5,6,7,7a,7b-六氢-6-羟基-1a-(1-(羟基甲基)乙烯基)-7,7a-二甲基-萘并(1,2-b)环氧乙烯-2(1aH)-酮
  参考文献：
  名称：

  病原性真菌合成含氧的双氧灵，巨人烯酮，磷烯酮和菜豆酮，植物毒素

  摘要：

  的几个氧化eremophilane倍半萜立体选择性合成如植物毒素，（+） - gigantenone 1，（+） - phomenone 2和（+） - phaseolinone 3，在短的步骤从实现（+） - sporogen-AO 1（13-desoxyphomenone）4。

  DOI：

  10.1016/s0040-4020(01)96908-x

文献信息

• Synthesis of Bioreductive Esters from Fungal Compounds
  作者：Natthida Weerapreeyakul、Rutchayaporn Anorach、Thidarut Khuansawad、Chavi Yenjai、Masahiko Isaka

  DOI：10.1248/cpb.55.930

  日期：——

  Four new bioreductive esters (7-10) have been synthesized. Their structures composed of trimethyl lock containing quinone propionic acid with an ester linkage to the fungal cytotoxic compounds; preussomerin G (1), preussomerin I (2), phaseolinone (3) and phomenone (4). The synthesized esters are aimed to act via reductive activation specifically at the cancer cells, resulting from hypoxia and overexpression

  已经合成了四种新的生物还原酯（7-10）。它们的结构由三甲基锁构成，该三锁含醌丙酸与真菌细胞毒性化合物具有酯键；preussomerin G（1），preussomerin I（2），phaseolinone（3）和phomenone（4）。合成的酯旨在通过还原性缺氧和过表达而通过还原性活化作用专门作用于癌细胞。因此，在整个正常细胞中分布期间，毒性将降低。在癌细胞系中使用已报道的还原酶（即BC-1细胞和NCI-H187）以及不含还原酶的癌细胞来确定其抗癌活性。KB单元格。当考虑每种细胞系时，结果表明结构修饰产生的7-10比其母体化合物（1-4）引起的细胞毒性更小。7和8对NCI-H187具有强烈的细胞毒性（IC50 <或= 5 microg / ml），而9和10对BC-1细胞具有中等的细胞毒性（IC50 = 6-10 microg / ml）。进一步研究了代表的酚酯（8）和​​醇酯（9）
• Studies on the Terpenoids and Related Alicyclic Compounds. XXIII. Total Syntheses of (±)-Phomenone, (±)-3-Epiphomenone, (±)-Ligularenolide, and (±)-Furanoligularanone
  作者：KOJI YAMAKAWA、MASATO KOBAYASHI、SHOTARO HINATA、TSUYOSHI SATOH

  DOI：10.1248/cpb.28.3265

  日期：——

  Total syntheses of (±)-phomenone (5a), (±)-3-epiphomenone (12), (±)-ligularenolide (27), and (±)-furanoligularanone (34) are described. Dehydration of 6 followed by epoxidation gave the epoxide (8), which was treated with lithium diethylamide to afford the alcohol (9). Epoxidation of 9 gave the α-epoxide (10), which was deketalized to give the diketone (11) Reduction of 11 with NaBH4 gave (±)-3-epiphomenone (12) as a major product. Stereoselective synthesis of (±)-5a starting from 7 was examined. Deketalization of 7 gave the triene-dione (13) which was reduced with NaBH4 to afford the alcohols 14a and 14b. Epoxidation of 3α-ol (14a) gave the epoxide (15), which was treated with lithium diethylamide to afford the diol (16). Epoxidation of 16 with hydrogen peroxide gave (±)-phomenone (5a) regio- and stereoselectively. Treatment of 17 with lithium diisopropylamide followed by condensation with methyl pyruvate gave the hydroxy ester (19), which was treated with acetic acid to give the ketone (24). 24 was thioketalized to give 25, which was treated with p-toluenesulfonic acid to afford the unsaturated lactone (26). 26 was transformed to (±)-ligularenolide (27) and (±)-tetrahydroligularenolide (28) in good yield. Condensation of 17 with acetol pyranyl ether followed by catalytic hydrogenation gave 33. Treatment of 33 with p-toluenesulfonic acid gave (±)-furanoligularanone (34), which was transformed to (±)-3β-furanoligularanol (36).

  描述了 (±)-phomenone (5a)、(±)-3-epiphomenone (12)、(±)-ligularenolide (27) 和 (±)-furanoligularanone (34) 的全合成。 6脱水，然后环氧化，得到环氧化物(8)，将其用二乙基氨基锂处理，得到醇(9)。 9的环氧化得到α-环氧化物(10)，将其去缩酮化得到二酮(11)。用NaBH 4 还原11得到(±)-3-epiphomenone(12)作为主要产物。检查了从7开始的(±)-5a的立体选择性合成。 7的脱缩酮得到三烯二酮(13)，将其用NaBH 4 还原得到醇14a和14b。 3α-醇(14a)的环氧化得到环氧化物(15)，将其用二乙基氨基锂处理得到二醇(16)。 16 用过氧化氢进行环氧化，区域选择性和立体选择性地生成 (±)-佛蒙酮 (5a)。用二异丙基氨基锂处理17，然后与丙酮酸甲酯缩合，得到羟基酯(19)，将其用乙酸处理，得到酮(24)。将24硫酮化得到25，将其用对甲苯磺酸处理得到不饱和内酯(26)。 26以良好的产率转化为(±)-木瓜烯内酯(27)和(±)-四氢木瓜烯内酯(28)。 17与丙酮醇吡喃基醚缩合，随后催化氢化，得到33。用对甲苯磺酸处理33，得到(±)-呋喃寡糖酮(34)，将其转化为(±)-3β-呋喃寡糖醇(36)。
• Stereostructure and formation mechanisn of a new substituted benzofuran from phomenone.
  作者：Renato Capasso、Giovanni Palumbo、Giacomino Randazzo、Alfonso Bavoso、Benedetto Di Blasio、Vincenzo Pavone

  DOI：10.1016/s0040-4020(01)87290-2

  日期：1986.1

  Phomenone, a known phytotoxic and mycotoxic sesquiterpene, afforded a new substituted benzofuran, by treatment with a H2SO4 in MeOH solution (10%). The structure of such compound, determined by spectroscopic and X-ray diffraction methods on its acetylderivative, is described. The formation mechanism of the new substituted benzofuran from the toxin is also discussed.

  通过用H 2 SO 4的MeOH溶液（10％）处理，已知的植物毒性和霉菌性倍半萜烯Phomnone提供了新的取代苯并呋喃。描述了通过光谱和X射线衍射法对其乙酰基衍生物确定的这种化合物的结构。还讨论了由毒素形成新的取代苯并呋喃的机理。