(2R,3S,4S,4aR,6S,8S,9S,9aS)-9-Benzyloxy-6-((2R,3S,5R,7R,8S)-7-benzyloxy-8-benzyloxymethyl-3-hydroxy-5-methyl-oxocan-2-ylmethyl)-2-[3-(tert-butyl-diphenyl-silanyloxy)-propyl]-3,4,8-trimethyl-hexahydro-1,5-dioxa-benzocyclohepten-7-one | 871912-74-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3S,4S,4aR,6S,8S,9S,9aS)-9-Benzyloxy-6-((2R,3S,5R,7R,8S)-7-benzyloxy-8-benzyloxymethyl-3-hydroxy-5-methyl-oxocan-2-ylmethyl)-2-[3-(tert-butyl-diphenyl-silanyloxy)-propyl]-3,4,8-trimethyl-hexahydro-1,5-dioxa-benzocyclohepten-7-one
• 英文别名: (2R,3S,4S,4aR,6S,8S,9S,9aS)-2-[3-[tert-butyl(diphenyl)silyl]oxypropyl]-6-[[(2R,3S,5R,7R,8S)-3-hydroxy-5-methyl-7-phenylmethoxy-8-(phenylmethoxymethyl)oxocan-2-yl]methyl]-3,4,8-trimethyl-9-phenylmethoxy-3,4,4a,8,9,9a-hexahydro-2H-pyrano[3,2-b]oxepin-7-one
• CAS: 871912-74-2
• 化学式: C₆₂H₈₀O₉Si
• 分子量: 997.397
• InChiKey: WPOQPDLZRWUBJK-DOYQPQFGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.68
• 重原子数：
  72
• 可旋转键数：
  20
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  102
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (2R,3S,4S,4aR,6S,8S,9S,9aS)-9-Benzyloxy-6-((2R,3S,5R,7R,8S)-7-benzyloxy-8-benzyloxymethyl-3-hydroxy-5-methyl-oxocan-2-ylmethyl)-2-[3-(tert-butyl-diphenyl-silanyloxy)-propyl]-3,4,8-trimethyl-hexahydro-1,5-dioxa-benzocyclohepten-7-one 在 三乙基硅烷 、 三氟甲磺酸三甲基硅酯 、 碘苯二乙酸 、 camphor-10-sulfonic acid 、 碘 作用下， 以 甲醇 、 二氯甲烷 、 环己烷 为溶剂， 反应 8.5h， 生成 (1R,3S,5S,7R,8S,10R,12S,14R,15S,16S,17R,19S,20S,21S)-5,15,16,21-tetramethyl-7,20-bis(phenylmethoxy)-8-(phenylmethoxymethyl)spiro[2,9,13,18-tetraoxatetracyclo[10.9.0.03,10.014,19]henicosane-17,2'-oxolane]
  参考文献：
  名称：

  Convergent synthesis of the IJKLM-ring part of ciguatoxin CTX3C

  摘要：

  Convergent synthesis of the IJKLM-ring part (2) of ciguatoxin CTX3C has been achieved from the I-ring and the L-ring parts (4 and 5) in total eight steps in 27% overall yield. The carbanion derived from 4, stabilized by a dimethyldithioacetal S-oxide group, was readily reacted with aldehyde 5 to give an adduct, which was facilely transformed into the corresponding alpha,epsilon-dihydroxy ketone 3. The JK-ring formation from 3 under reductive conditions followed by oxidative M-ring cyclization efficiently led to the pentacyclic ether 2. Improved synthesis of 6, a synthetic intermediate for 4, was also established. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.09.164
• 作为产物：
  描述：

  (2R,4aR,6S,7R,9S,10aS)-6-[[tert-butyl(diphenyl)silyl]oxymethyl]-9-methyl-2-phenyl-4,4a,6,7,8,9,10,10a-octahydro-[1,3]dioxino[5,4-b]oxocin-7-ol 在 咪唑 、 2,6-二甲基吡啶 、 三乙基硅烷 、 ethandithiol 、 lithium aluminium tetrahydride 、 三氯化铝 、 草酰氯 、 三氟甲磺酸三甲基硅酯 、 三氟化硼乙醚 、 potassium tert-butylate 、 四丁基氟化铵 、 sodium hexamethyldisilazane 、 4-甲基苯磺酸吡啶 、 四丁基碘化铵 、 二甲基亚砜 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 18.84h， 生成 (2R,3S,4S,4aR,6S,8S,9S,9aS)-9-Benzyloxy-6-((2R,3S,5R,7R,8S)-7-benzyloxy-8-benzyloxymethyl-3-hydroxy-5-methyl-oxocan-2-ylmethyl)-2-[3-(tert-butyl-diphenyl-silanyloxy)-propyl]-3,4,8-trimethyl-hexahydro-1,5-dioxa-benzocyclohepten-7-one
  参考文献：
  名称：

  Convergent synthesis of the IJKLM-ring part of ciguatoxin CTX3C

  摘要：

  Convergent synthesis of the IJKLM-ring part (2) of ciguatoxin CTX3C has been achieved from the I-ring and the L-ring parts (4 and 5) in total eight steps in 27% overall yield. The carbanion derived from 4, stabilized by a dimethyldithioacetal S-oxide group, was readily reacted with aldehyde 5 to give an adduct, which was facilely transformed into the corresponding alpha,epsilon-dihydroxy ketone 3. The JK-ring formation from 3 under reductive conditions followed by oxidative M-ring cyclization efficiently led to the pentacyclic ether 2. Improved synthesis of 6, a synthetic intermediate for 4, was also established. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2005.09.164

文献信息

• Convergent synthesis of the IJKLM-ring part of ciguatoxin CTX3C
  作者：Daisuke Domon、Kenshu Fujiwara、Akio Murai、Hidethoshi Kawai、Takanori Suzuki

  DOI：10.1016/j.tetlet.2005.09.164

  日期：2005.11

  Convergent synthesis of the IJKLM-ring part (2) of ciguatoxin CTX3C has been achieved from the I-ring and the L-ring parts (4 and 5) in total eight steps in 27% overall yield. The carbanion derived from 4, stabilized by a dimethyldithioacetal S-oxide group, was readily reacted with aldehyde 5 to give an adduct, which was facilely transformed into the corresponding alpha,epsilon-dihydroxy ketone 3. The JK-ring formation from 3 under reductive conditions followed by oxidative M-ring cyclization efficiently led to the pentacyclic ether 2. Improved synthesis of 6, a synthetic intermediate for 4, was also established. (c) 2005 Elsevier Ltd. All rights reserved.