methyl 2-[(2S,3R,4S,4aS,6R,8aS)-2-[(1S)-6-[(2S,5S)-5-[2-[(2S,4R,6R)-6-[[(2S,3R,4R,4aS,6R,7R,8aS)-7-[tert-butyl(dimethyl)silyl]oxy-6-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-3-[(4-methoxyphenyl)methoxy]-4-methyl-2,3,4,4a,6,7,8,8a-octahydropyrano[3,2-b]pyran-2-yl]methyl]-4-methyl-5-methylideneoxan-2-yl]ethyl]-4-methylideneoxolan-2-yl]-1-[tert-butyl(dimethyl)silyl]oxy-4-hydroxyhex-2-ynyl]-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-2,3,4,4a,6,7,8,8a-octahydropyrano[3,2-b]pyran-6-yl]acetate | 1353269-15-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-[(2S,3R,4S,4aS,6R,8aS)-2-[(1S)-6-[(2S,5S)-5-[2-[(2S,4R,6R)-6-[[(2S,3R,4R,4aS,6R,7R,8aS)-7-[tert-butyl(dimethyl)silyl]oxy-6-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-3-[(4-methoxyphenyl)methoxy]-4-methyl-2,3,4,4a,6,7,8,8a-octahydropyrano[3,2-b]pyran-2-yl]methyl]-4-methyl-5-methylideneoxan-2-yl]ethyl]-4-methylideneoxolan-2-yl]-1-[tert-butyl(dimethyl)silyl]oxy-4-hydroxyhex-2-ynyl]-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-2,3,4,4a,6,7,8,8a-octahydropyrano[3,2-b]pyran-6-yl]acetate
• CAS: 1353269-15-4
• 化学式: C₈₁H₁₄₄O₁₆Si₅
• 分子量: 1514.45
• InChiKey: FBBZFCMAHDLZCD-UAXIDMKZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.37
• 重原子数：
  102
• 可旋转键数：
  33
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  167
• 氢给体数：
  1
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  methyl 2-[(2S,3R,4S,4aS,6R,8aS)-2-[(1S)-6-[(2S,5S)-5-[2-[(2S,4R,6R)-6-[[(2S,3R,4R,4aS,6R,7R,8aS)-7-[tert-butyl(dimethyl)silyl]oxy-6-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-3-[(4-methoxyphenyl)methoxy]-4-methyl-2,3,4,4a,6,7,8,8a-octahydropyrano[3,2-b]pyran-2-yl]methyl]-4-methyl-5-methylideneoxan-2-yl]ethyl]-4-methylideneoxolan-2-yl]-1-[tert-butyl(dimethyl)silyl]oxy-4-hydroxyhex-2-ynyl]-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-2,3,4,4a,6,7,8,8a-octahydropyrano[3,2-b]pyran-6-yl]acetate 在 碳酸氢钠 、 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 0.83h， 以94%的产率得到
  参考文献：
  名称：

  Total Synthesis of Halichondrin C

  摘要：

  The first total synthesis of halichondrin C has been completed, highlighted by development of the synthetic method to construct the C8-C14 polycycle. Cr-mediated coupling reactions are used seven times to form a new C C bond. The acid stability of halichondrin C is studied, demonstrating that the macrolactone stabilizes the C8-C14 polycycle, relative to the one present in the C1-C16 model.

  DOI：

  10.1021/ja2108307
• 作为产物：
  描述：

  3-[(2S,5S)-5-[2-[(2S,4R,6R)-6-[[(2S,3R,4R,4aS,6R,7R,8aS)-7-[tert-butyl(dimethyl)silyl]oxy-6-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-3-[(4-methoxyphenyl)methoxy]-4-methyl-2,3,4,4a,6,7,8,8a-octahydropyrano[3,2-b]pyran-2-yl]methyl]-4-methyl-5-methylideneoxan-2-yl]ethyl]-4-methylideneoxolan-2-yl]propanal 、 methyl 2-[(2S,3R,4S,4aS,6R,8aS)-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-2-[(1S)-1-[tert-butyl(dimethyl)silyl]oxy-3-iodoprop-2-ynyl]-2,3,4,4a,6,7,8,8a-octahydropyrano[3,2-b]pyran-6-yl]acetate 在 chromium dichloride 、 锰 、 二氯二茂锆 、 (S)-N-(2-(4-isopropyl-4,5-dihydrooxazol-2-yl)-6-methoxyphenyl)methanesulfonamide 、 NiCl₂*2,9-diethyl-1,10-phenanthroline complex 、 1,8-双二甲氨基萘 、 lithium chloride 作用下， 以 乙腈 为溶剂， 反应 3.0h， 以85%的产率得到methyl 2-[(2S,3R,4S,4aS,6R,8aS)-2-[(1S)-6-[(2S,5S)-5-[2-[(2S,4R,6R)-6-[[(2S,3R,4R,4aS,6R,7R,8aS)-7-[tert-butyl(dimethyl)silyl]oxy-6-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-3-[(4-methoxyphenyl)methoxy]-4-methyl-2,3,4,4a,6,7,8,8a-octahydropyrano[3,2-b]pyran-2-yl]methyl]-4-methyl-5-methylideneoxan-2-yl]ethyl]-4-methylideneoxolan-2-yl]-1-[tert-butyl(dimethyl)silyl]oxy-4-hydroxyhex-2-ynyl]-3,4-bis[[tert-butyl(dimethyl)silyl]oxy]-2,3,4,4a,6,7,8,8a-octahydropyrano[3,2-b]pyran-6-yl]acetate
  参考文献：
  名称：

  Total Synthesis of Halichondrin C

  摘要：

  The first total synthesis of halichondrin C has been completed, highlighted by development of the synthetic method to construct the C8-C14 polycycle. Cr-mediated coupling reactions are used seven times to form a new C C bond. The acid stability of halichondrin C is studied, demonstrating that the macrolactone stabilizes the C8-C14 polycycle, relative to the one present in the C1-C16 model.

  DOI：

  10.1021/ja2108307

文献信息

• Total Synthesis of Halichondrin C
  作者：Akihiko Yamamoto、Atsushi Ueda、Paul Brémond、Paolo S. Tiseni、Yoshito Kishi

  DOI：10.1021/ja2108307

  日期：2012.1.18

  The first total synthesis of halichondrin C has been completed, highlighted by development of the synthetic method to construct the C8-C14 polycycle. Cr-mediated coupling reactions are used seven times to form a new C C bond. The acid stability of halichondrin C is studied, demonstrating that the macrolactone stabilizes the C8-C14 polycycle, relative to the one present in the C1-C16 model.