[(1S)-2-[tert-butyl(diphenyl)silyl]oxy-1-[(2S,3S,6R,8R,9S)-3-methoxy-9-methyl-8-(2-oxoethyl)-1,7-dioxaspiro[5.5]undec-10-en-2-yl]ethyl] 2,2-dimethylpropanoate | 1032880-17-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [(1S)-2-[tert-butyl(diphenyl)silyl]oxy-1-[(2S,3S,6R,8R,9S)-3-methoxy-9-methyl-8-(2-oxoethyl)-1,7-dioxaspiro[5.5]undec-10-en-2-yl]ethyl] 2,2-dimethylpropanoate
• CAS: 1032880-17-3
• 化学式: C₃₆H₅₀O₇Si
• 分子量: 622.874
• InChiKey: JZTXAOGLWPAJMV-UMFYWIAMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.59
• 重原子数：
  44
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [(1S)-2-[tert-butyl(diphenyl)silyl]oxy-1-[(2S,3S,6R,8R,9S)-3-methoxy-9-methyl-8-(2-oxoethyl)-1,7-dioxaspiro[5.5]undec-10-en-2-yl]ethyl] 2,2-dimethylpropanoate 在 三氟化硼乙醚 、 4-甲基苯磺酸吡啶 、 溶剂黄146 、 tetramethylammonium triacetoxyborohydride 作用下， 以 二氯甲烷 、 丙酮 、 乙腈 为溶剂， 反应 14.0h， 生成 (S)-2-((tert-butyldiphenylsilyl)oxy)-1-((2S,3S,6R,8R,9S)-8-(((4S,6S)-2,2-dimethyl-6-(((2S,6R)-6-(2-(pivaloyloxy)ethyl)tetrahydro-2H-pyran-2-yl)methyl)-1,3-dioxan-4-yl)methyl)-3-methoxy-9-methyl-1,7-dioxaspiro[5.5]undec-10-en-2-yl)ethyl pivalate
  参考文献：
  名称：

  ASSEMBLY OF THE SOUTHERN MACROCYCLIC HALF OF (+)-SPIRASTRELLOLIDE A THROUGH CYCLIC ACETAL TETHERED RING-CLOSING METATHESIS AND 1,3-ANTI-MUKAIYAMA-ALDOL

  摘要：

  We describe herein details of our efforts in syntheses of A-ring and BC-ring of (+)-spirastrellolide A. While the former would constitute a facile 12-step synthetic endeavor starting from 1,5-pentanediol, the latter would showcase a cyclic acetal-tethered ring-closing metathesis [RCM] method that was developed in our lab for de novo synthesis of spiroketals. Constructing the entire Southern Half of the macrocycle would require 1,3-anti-Mukaiyama aldol addition for connecting A-ring and BC-ring specifically at C10 and C11, thereby culminating a 17-step approach for the Southern Macrocyclic Half linearly from (+)-2,3-(O)-iso-propylidene-L-threitol. Also discussed here is the possibility of pursuing a more convergent approach toward the assembly of the Southern Half through first connecting A-ring and C-ring via acetal formation that would first link together the free C13-OH with C17 at the spiro-BC-ring junction. An ensuing application of our cyclic acetal-tethered RCM strategy to close B-ring would adopt this cyclic acetal intermediate.

  DOI：

  10.3987/com-12-s(n)54
• 作为产物：
  描述：

  4-O-(tert-butyldiphenylsilyl)-2,3-O-isopropylidene-L-threitol 在 吡啶 、 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 4-二甲氨基吡啶 、 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 (-)-B-methoxydiisopinocamphenylborane 、 三氧化硫吡啶 、 sodium hydride 、 对甲苯磺酸 、 二甲基亚砜 、 三乙胺 、 9-硼双环[3.3.1]壬烷 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 、 甲苯 、 叔丁醇 为溶剂， 反应 44.53h， 生成 [(1S)-2-[tert-butyl(diphenyl)silyl]oxy-1-[(2S,3S,6R,8R,9S)-3-methoxy-9-methyl-8-(2-oxoethyl)-1,7-dioxaspiro[5.5]undec-10-en-2-yl]ethyl] 2,2-dimethylpropanoate
  参考文献：
  名称：

  ASSEMBLY OF THE SOUTHERN MACROCYCLIC HALF OF (+)-SPIRASTRELLOLIDE A THROUGH CYCLIC ACETAL TETHERED RING-CLOSING METATHESIS AND 1,3-ANTI-MUKAIYAMA-ALDOL

  摘要：

  We describe herein details of our efforts in syntheses of A-ring and BC-ring of (+)-spirastrellolide A. While the former would constitute a facile 12-step synthetic endeavor starting from 1,5-pentanediol, the latter would showcase a cyclic acetal-tethered ring-closing metathesis [RCM] method that was developed in our lab for de novo synthesis of spiroketals. Constructing the entire Southern Half of the macrocycle would require 1,3-anti-Mukaiyama aldol addition for connecting A-ring and BC-ring specifically at C10 and C11, thereby culminating a 17-step approach for the Southern Macrocyclic Half linearly from (+)-2,3-(O)-iso-propylidene-L-threitol. Also discussed here is the possibility of pursuing a more convergent approach toward the assembly of the Southern Half through first connecting A-ring and C-ring via acetal formation that would first link together the free C13-OH with C17 at the spiro-BC-ring junction. An ensuing application of our cyclic acetal-tethered RCM strategy to close B-ring would adopt this cyclic acetal intermediate.

  DOI：

  10.3987/com-12-s(n)54

文献信息

• Synthesis of the C1−C23 Fragment of Spirastrellolide A
  作者：Jin-Haek Yang、Jia Liu、Richard P. Hsung

  DOI：10.1021/ol8008057

  日期：2008.6.1

  Synthesis of the C1-C23 fragment in spirastrellolide A is described, featuring a cyclic acetal-tethered RCM for stereoselective constructions of spiroketal, and a 1,3-anti aldol involving methyl ketone enolate and Mukaiyama conditions.
• ASSEMBLY OF THE SOUTHERN MACROCYCLIC HALF OF (+)-SPIRASTRELLOLIDE A THROUGH CYCLIC ACETAL TETHERED RING-CLOSING METATHESIS AND 1,3-ANTI-MUKAIYAMA-ALDOL
  作者：Richard P. Hsung、Yu Tang、Jin-Haek Yang、Jia Liu、Chao-Chao Wang、Ming-Can Lv、Yi-Biao Wu、Xue-Liang Yu、Changhong Ko

  DOI：10.3987/com-12-s(n)54

  日期：——

  We describe herein details of our efforts in syntheses of A-ring and BC-ring of (+)-spirastrellolide A. While the former would constitute a facile 12-step synthetic endeavor starting from 1,5-pentanediol, the latter would showcase a cyclic acetal-tethered ring-closing metathesis [RCM] method that was developed in our lab for de novo synthesis of spiroketals. Constructing the entire Southern Half of the macrocycle would require 1,3-anti-Mukaiyama aldol addition for connecting A-ring and BC-ring specifically at C10 and C11, thereby culminating a 17-step approach for the Southern Macrocyclic Half linearly from (+)-2,3-(O)-iso-propylidene-L-threitol. Also discussed here is the possibility of pursuing a more convergent approach toward the assembly of the Southern Half through first connecting A-ring and C-ring via acetal formation that would first link together the free C13-OH with C17 at the spiro-BC-ring junction. An ensuing application of our cyclic acetal-tethered RCM strategy to close B-ring would adopt this cyclic acetal intermediate.