(4R,5R,8R)-1,8-di{[tert-butyl(dimethyl)silyl]oxy}-5-{[tert-butyl(diphenyl)silyl]oxy}-12-[(para-methoxybenzyl)oxy]dodec-6-yn-4-ol

• 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: (4R,5R,8R)-1,8-di{[tert-butyl(dimethyl)silyl]oxy}-5-{[tert-butyl(diphenyl)silyl]oxy}-12-[(para-methoxybenzyl)oxy]dodec-6-yn-4-ol
• 英文别名: (4R,5R,8R)-1,8-bis[[tert-butyl(dimethyl)silyl]oxy]-5-[tert-butyl(diphenyl)silyl]oxy-12-[(4-methoxyphenyl)methoxy]dodec-6-yn-4-ol
• 化学式: C₄₈H₇₆O₆Si₃
• 分子量: 833.384
• InChiKey: AWYBRUBFTYYNPB-YMYISXBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.88
• 重原子数：
  57
• 可旋转键数：
  23
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (4R,5R,8R)-1,8-di{[tert-butyl(dimethyl)silyl]oxy}-5-{[tert-butyl(diphenyl)silyl]oxy}-12-[(para-methoxybenzyl)oxy]dodec-6-yn-4-ol 、 二甲醇缩甲醛 在 对甲苯磺酸 、 lithium bromide 作用下， 反应 96.0h， 以82%的产率得到(4R,5R,8R)-1,8-di{[tert-butyl(dimethyl)silyl]oxy}-5-{[tert-butyl(diphenyl)silyl]oxy}-12-[(para-methoxybenzyl)oxy]-4-(methoxymethoxy)dodec-6-yne
  参考文献：
  名称：

  A concise route to the C3–C23 fragment of the macrolide palmerolide A

  摘要：

  A concise route to the C3-C23 part of the macrolide palmerolide A was developed. This part features the 7,10,11-trihydroxy sector containing the 8E-double bond as well as the 14,16-diene subunit. The stereocenter at C-7 originated from a Noyori reduction on alkynone 8. The substrate 16 containing an enyne was obtained via a Claisen rearrangement. The vicinal diol at C10,C11 was created by a Sharpless asymmetric dihydroxylation. After selective protecting group manipulations the propargylic alcohol was reduced with Red-Al to the E-alkylic alcohol 26. The conjugated diene in the fragment 40 resulted from a Stille cross-coupling reaction between the vinylstarmane derived from alkyne 30 and the vinyl iodide 39. The latter could conveniently be prepared by an aldol/Wittig strategy. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.10.028
• 作为产物：
  描述：

  (4R,5R,8R)-1,8-di{[tert-butyl(dimethyl)silyl]oxy}-12-[(para-methoxybenzyl)oxy]dodec-6-yne-4,5-diol 、 叔丁基二苯基氯硅烷 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以75%的产率得到(4R,5R,8R)-1,8-di{[tert-butyl(dimethyl)silyl]oxy}-5-{[tert-butyl(diphenyl)silyl]oxy}-12-[(para-methoxybenzyl)oxy]dodec-6-yn-4-ol
  参考文献：
  名称：

  A concise route to the C3–C23 fragment of the macrolide palmerolide A

  摘要：

  A concise route to the C3-C23 part of the macrolide palmerolide A was developed. This part features the 7,10,11-trihydroxy sector containing the 8E-double bond as well as the 14,16-diene subunit. The stereocenter at C-7 originated from a Noyori reduction on alkynone 8. The substrate 16 containing an enyne was obtained via a Claisen rearrangement. The vicinal diol at C10,C11 was created by a Sharpless asymmetric dihydroxylation. After selective protecting group manipulations the propargylic alcohol was reduced with Red-Al to the E-alkylic alcohol 26. The conjugated diene in the fragment 40 resulted from a Stille cross-coupling reaction between the vinylstarmane derived from alkyne 30 and the vinyl iodide 39. The latter could conveniently be prepared by an aldol/Wittig strategy. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.10.028

文献信息

• A concise route to the C3–C23 fragment of the macrolide palmerolide A
  作者：Julia Jägel、Anke Schmauder、Michael Binanzer、Martin E. Maier

  DOI：10.1016/j.tet.2007.10.028

  日期：2007.12

  A concise route to the C3-C23 part of the macrolide palmerolide A was developed. This part features the 7,10,11-trihydroxy sector containing the 8E-double bond as well as the 14,16-diene subunit. The stereocenter at C-7 originated from a Noyori reduction on alkynone 8. The substrate 16 containing an enyne was obtained via a Claisen rearrangement. The vicinal diol at C10,C11 was created by a Sharpless asymmetric dihydroxylation. After selective protecting group manipulations the propargylic alcohol was reduced with Red-Al to the E-alkylic alcohol 26. The conjugated diene in the fragment 40 resulted from a Stille cross-coupling reaction between the vinylstarmane derived from alkyne 30 and the vinyl iodide 39. The latter could conveniently be prepared by an aldol/Wittig strategy. (c) 2007 Elsevier Ltd. All rights reserved.