methyl (Z,3S,5R)-[3,5-bis(tert-butyldimethylsilyl)oxy-2-methylenecyclohexylidene]acetate | 129482-80-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: methyl (Z,3S,5R)-[3,5-bis(tert-butyldimethylsilyl)oxy-2-methylenecyclohexylidene]acetate
• 英文别名: (3S-(1Z,3α,5β))-(3,5-Bis{[(1,1-dimethylethyl)dimethylsilyl]oxy}-2-methylenecyclohexylidene)acetic acid methyl ester；Z-(3S,5R)-[3,5-bis-(tert-butyl-dimethyl-silanyloxy)-2-methylene-cyclohexylidene]-acetic acid methyl ester；methyl (2Z)-2-[(3S,5R)-3,5-bis[[tert-butyl(dimethyl)silyl]oxy]-2-methylidenecyclohexylidene]acetate
• CAS: 129482-80-0
• 化学式: C₂₂H₄₂O₄Si₂
• 分子量: 426.744
• InChiKey: NRFMPIHOIWJPLB-HICHHZPXSA-N

物化性质

• 沸点：
  419.7±45.0 °C(Predicted)
• 密度：
  0.95±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.22
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl (Z,3S,5R)-[3,5-bis(tert-butyldimethylsilyl)oxy-2-methylenecyclohexylidene]acetate 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 以87%的产率得到
  参考文献：
  名称：

  通过化学酶法对维生素D3代谢产物的A环合成子进行对映选择性合成

  摘要：

  具有1α羟基的维生素D 3代谢物的A环合成子是从酶促生成的手性单酯6开始合成的。

  DOI：

  10.1016/0040-4039(90)80021-d
• 作为产物：
  描述：

  (S)-4-Bromo-3-hydroxy-4-pentenoic acid (S)-1,2,2-triphenyl-2-hydroxyethyl ester 在 palladium diacetate 、 三苯基膦 咪唑 、 18-冠醚-6 、 Zeolite 3 Angstroem 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 potassium carbonate 、 pyridinium chlorochromate 、 magnesium bromide 、 lithium diisopropyl amide 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 6.83h， 生成 methyl (Z,3S,5R)-[3,5-bis(tert-butyldimethylsilyl)oxy-2-methylenecyclohexylidene]acetate
  参考文献：
  名称：

  An efficient asymmetric synthesis of 1.alpha.,25-(OH)2 vitamin D3 A-ring synthon

  摘要：

  Chiral synthesis of the A-ring synthon 3 of 1alpha,25-dihydroxyvitamin D3 (1a) based on palladium-catalyzed cyclization of 8-bromo-2,8-nonadienoates is described. Reaction of (E)-4b and (Z)-4d in the presence of Pd(OAc)2, PPh3, and K2CO3 gave (E)-3b and (Z)-3d, respectively. Optically active 4d was prepared from 24 by asymmetric aldol reaction using 31, which was cyclized to 3d. With further reactions, 1alpha,25-dihydroxyvitamin D3 (1a) was obtained.

  DOI：

  10.1021/jo00061a028

文献信息

• Efficient and versatile synthesis of a-ring precursors of 1α,25-dihydroxy-vitamin D3 and analogues. Application to the synthesis of Lythgoe-Roche phosphine oxide
  作者：Antonio Mouriño、Mercedes Torneiro、Cristian Vitale、Sara Fernández、José Pérez-Sestelo、Sofia Anné、Carlos Gregorio

  DOI：10.1016/s0040-4039(97)01005-8

  日期：1997.6

  An efficient, versatile synthesis of Lythgoe-Phosphine Oxide has been developed starting from l-carvone. The key steps are rupture of protected epoxide 7 to give dicarbonyl compound 8, preparation of vinylic triflate 2, and palladium-catalysed cyclization-carbonylation of vinylic triflate 2.

  从1-香芹酮开始开发了有效的，多功能的Lythgoe-膦氧化物的合成方法。关键步骤是使受保护的环氧化物7断裂，得到二羰基化合物8；制备三氟乙烯磺酸乙烯酯2；以及钯催化的三氟乙烯磺酸乙烯酯2的环化羰基化反应。
• Vitamin D3 analogs
  申请人：Hoffmann-La Roche Inc.

  公开号：US06331642B1

  公开（公告）日：2001-12-18

  Compounds of the formula wherein R1 is hydrogen or an alkyl group; R2 is hydrogen or an alkyl group; or R1, R2 and C20 together are cyclopropyl; R3 is alkyl, hydroxy-alkyl or fluoroalkyl; and R4 is alkyl, hydroxy-alkyl or fluoroalkyl which are useful in the treatment of breast cancer, prostate cancer, myeloid leukemia benign prostate growth, baldness and osteoporosis.

  该式化合物中，其中R1是氢或烷基；R2是氢或烷基；或R1，R2和C20一起是环丙基；R3是烷基，羟基烷基或氟烷基；R4是烷基，羟基烷基或氟烷基，可用于治疗乳腺癌、前列腺癌、骨髓性白血病、良性前列腺增生、脱发和骨质疏松症。
• Synthesis and evaluation of A-Ring diastereomers of 1α,25-dihydroxy-22-oxavitamin D 3 (OCT) 1
  作者：Susumi Hatakeyama、Toshio Okano、Junji Maeyama、Tomoyuki Esumi、Hiroko Hiyamizu、Yoshiharu Iwabuchi、Kimie Nakagawa、Keiichi Ozono、Akira Kawase、Noboru Kubodera

  DOI：10.1016/s0968-0896(00)00259-5

  日期：2001.2

  A-ring diastereomers of 1 alpha ,25-dihydroxy-22-oxavitamin D-3 (OCT) (2), 3-epi-1 alpha ,25-dihydroxy-22-oxavitamin D-3 (3-epiOCT) (3) and 1,3-diepi-1 alpha ,25-dihydroxy-22-oxavitamin D-3 (1,3-diepiOCT) (4) were synthesized by the convergent method. In vitro binding affinity for rat vitamin D binding protein and calf-thymus vitamin D receptor, differentiation-inducing activity on HL-60 cells, and transcriptional activity of 3-epiOCT (3) and 1,3-diepiOCT (4) were evaluated in comparison with OCT (2), 1-epi-1 alpha ,25-dihydroxy-22-oxavitamin D-3 (1-epiOCT) (5) and 1 alpha ,25-dihydroxyvitamin D-3 (1). (C) 2001 Elsevier Science Ltd. All rights reserved.
• Stereoselective synthesis of 1α-hydroxyvitamin D3 A-ring synthons by palladium-catalyzed cyclization
  作者：Kazuo Nagasawa、Yoshiro Zako、Hideki Ishihara、Isao Shimizu

  DOI：10.1016/s0040-4039(00)93501-9

  日期：1991.9

  Palladium-catalyzed cyclization of 8-bromo-2,8-nonadienoates proceeded stereoselectively to give 1-alpha-hydroxyvitamin D3 A-ring synthons in good yields.
• J. Org. Chem. 1986, 51, 3098-3108
  作者：

  DOI：——

  日期：——