(2S,3S,4S,6R,8S,9S)-3,9-dimethyl-8-<(R)-2-<(tert-butyldimethylsilyl)oxy>-1-propyl>-2-<(R)-3-<<(4-methoxyphenyl)methoxy>methyl>-1-pentyl>-1,7-dioxaspiro<5.5>undecan-4-ol | 131685-66-0

• 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: (2S,3S,4S,6R,8S,9S)-3,9-dimethyl-8-<(R)-2-<(tert-butyldimethylsilyl)oxy>-1-propyl>-2-<(R)-3-<<(4-methoxyphenyl)methoxy>methyl>-1-pentyl>-1,7-dioxaspiro<5.5>undecan-4-ol
• 英文别名: (2S,3S,4S,6R,8S,9S)-3,9-dimethyl-8-[(R)-2-[(tert-butyldimethylsilyl)oxy]-1-propyl]-2-{(R)-3-[[(4-methoxyphenyl)methoxy]methyl]-1-pentyl}-1,7-dioxaspiro[5.5]undecan-4-ol；(2S,3S,6R,8S,9S,10S)-2-[(2R)-2-[tert-butyl(dimethyl)silyl]oxypropyl]-8-[(3R)-3-[(4-methoxyphenyl)methoxymethyl]pentyl]-3,9-dimethyl-1,7-dioxaspiro[5.5]undecan-10-ol
• CAS: 131685-66-0
• 化学式: C₃₄H₆₀O₆Si
• 分子量: 592.932
• InChiKey: OPDAXLZPXOVWNE-DQSIKCDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.12
• 重原子数：
  41
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  (2S,3S,4S,6R,8S,9S)-3,9-dimethyl-8-<(R)-2-<(tert-butyldimethylsilyl)oxy>-1-propyl>-2-<(R)-3-<<(4-methoxyphenyl)methoxy>methyl>-1-pentyl>-1,7-dioxaspiro<5.5>undecan-4-ol 在 4-二甲氨基吡啶 、 lithium hydroxide 、 氢氟酸 、 水 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 61.5h， 生成 (2S,3S,4S,6R,8S,9S)-3,9-dimethyl-8-[(R)-2-hydroxy-1-propyl]-2-[(R)-3-(hydroxymethyl)-1-pentyl]-1,7-dioxaspiro[5.5]undecan-4-ol
  参考文献：
  名称：

  Assignment of stereochemistry in the oligomycin/rutamycin/cytovaricin family of antibiotics. Asymmetric synthesis of the rutamycin spiroketal synthon

  摘要：

  The absolute stereochemistry of the rutamycin antibiotics 2a,b has been established through asymmetric synthesis of the known degradation product 4. One of the key steps in the assemblage process involves acylation of the metalated hydrazone 6 with the N-methoxy-N-methyl amide 5. Both of these enantiomerically pure intermediates have been prepared in good overall yield and high diastereoselectivity (de > 94%). All absolute stereochemical relationships were established through alkylation and aldol bond constructions using N-acyloxazolidinone chiral auxiliaries. Subjection of 17 to acid hydrolysis/deprotection resulted in loss of protecting groups and subsequent spiroketalization to 19 (80%). Silylation of the secondary alcohol in 19 was followed by a samarium-catalyzed Meerwein-Ponndorf-Verley reduction to provide the equatorial alcohol 20 in excellent yield and stereoselectivity (de = 97%). Control experiments indicate that this surprisingly stereoselective reaction operates under kinetic control and that the observed stereochemical outcome may be the result of coordination of the reactive reducing agent to the axial spiroketal oxygen. Conversion of 20 to triol 4 afforded material that is identical with the rutamycin degradation product in all respects. These results establish that the absolute stereochemistry of the rutamycins is as shown (2a,b).

  DOI：

  10.1021/jo00313a011
• 作为产物：
  描述：

  (2S,3R,6R,8S,9S)-3,9-dimethyl-8-<(R)-2-<(tert-butyldimethylsilyl)oxy>-1-propyl>-2-<(R)-3-<<(4-methoxyphenyl)methoxy>methyl>-1-pentyl>-1,7-dioxaspiro<5.5>undecan-4-one 生成 (2S,3S,4S,6R,8S,9S)-3,9-dimethyl-8-<(R)-2-<(tert-butyldimethylsilyl)oxy>-1-propyl>-2-<(R)-3-<<(4-methoxyphenyl)methoxy>methyl>-1-pentyl>-1,7-dioxaspiro<5.5>undecan-4-ol
  参考文献：
  名称：

  EVANS, DAVID A.;RIEGER, DALE L.;JONES, TODD K.;KALDOR, STEPHEN W., J. ORG. CHEM., 55,(1990) N6, C. 6260-6268

  摘要：

  DOI：

文献信息

• Total Synthesis of Rutamycin B, a Macrolide Antibiotic from <i>Streptomyces </i><i>a</i><i>ureofaciens</i>
  作者：James D. White、Roger Hanselmann、Randy W. Jackson、Warren J. Porter、Yoshihiro Ohba、Thomas Tiller、Shan Wang

  DOI：10.1021/jo0104429

  日期：2001.7.1

  Rutamycin B (2) was synthesized from three principal subunits, spiroketal 75, keto aldehyde 83, and aldehyde 108. First, triol 62 was assembled by Julia coupling of sulfone 56 with aldehyde 58 followed by an acid-catalyzed spiroketalization. The three hydroxyl functions of 62 were successfully differentiated, leading to phosphonate 75. The latter was condensed in a Wadsworth-Emmons reaction with 83

  Rutamycin B（2）由三个主要的亚基螺环酮75，酮醛83和醛108合成。首先，三元醇62通过砜56与醛58的茱莉亚偶联反应组装，然后进行酸催化的螺酮缩合。成功区分了62个化合物的三个羟基官能团，生成了膦酸酯75。后者在Wadsworth-Emmons反应中与从（R）-醛76分六步制得的83缩合，得到92。 92和108在严格取决于醛中对-甲氧基苄基醚的存在的过程中提供了具有高立体选择性的Felkin产物109。109通过醛116转化为乙烯基硼酸酯122，然后在Suzuki条件下进行大环化，得到123。对其进行彻底的脱甲硅烷基化得到芸霉素B。
• Total synthesis of the macrolide antibiotic rutamycin B
  作者：David A. Evans、Howard P. Ng、Dale L. Rieger

  DOI：10.1021/ja00077a049

  日期：1993.12

  A convergent asymmetric synthesis of the macrolide antibiotic rutamycin B has been achieved through the synthesis and coupling of its spiroketal and polypropionate subunits. Both fragments were constructed utilizing auxiliary-based asymmetric aldol had alkylation reactions to control the absolute stereochemical relationships. The polypropionate fragment was assembled from its C 1 -C 8 and C 9 -C 17

  通过其螺缩酮和聚丙酸酯亚基的合成和偶联，实现了大环内酯类抗生素芦他霉素 B 的会聚不对称合成。两个片段都是利用基于辅助的不对称羟醛构建的，具有烷基化反应以控制绝对立体化学关系。聚丙酸酯片段由其 C 1 -C 8 和 C 9 -C 17 亚基组装而成，这些亚基通过非对映选择性、错配、双立体区分醛醇反应连接。螺缩酮亚基和聚丙酸酯亚基的结合是通过 Suzuki 偶联完成的，提供了直接获取芦他霉素 seco 酸的途径，该酸以高产率环化为受保护的大环内酯
• EVANS, DAVID A.;RIEGER, DALE L.;JONES, TODD K.;KALDOR, STEPHEN W., J. ORG. CHEM., 55,(1990) N6, C. 6260-6268
  作者：EVANS, DAVID A.、RIEGER, DALE L.、JONES, TODD K.、KALDOR, STEPHEN W.

  DOI：——

  日期：——
• Assignment of stereochemistry in the oligomycin/rutamycin/cytovaricin family of antibiotics. Asymmetric synthesis of the rutamycin spiroketal synthon
  作者：David A. Evans、Dale L. Rieger、Todd K. Jones、Stephen W. Kaldor

  DOI：10.1021/jo00313a011

  日期：1990.12

  The absolute stereochemistry of the rutamycin antibiotics 2a,b has been established through asymmetric synthesis of the known degradation product 4. One of the key steps in the assemblage process involves acylation of the metalated hydrazone 6 with the N-methoxy-N-methyl amide 5. Both of these enantiomerically pure intermediates have been prepared in good overall yield and high diastereoselectivity (de > 94%). All absolute stereochemical relationships were established through alkylation and aldol bond constructions using N-acyloxazolidinone chiral auxiliaries. Subjection of 17 to acid hydrolysis/deprotection resulted in loss of protecting groups and subsequent spiroketalization to 19 (80%). Silylation of the secondary alcohol in 19 was followed by a samarium-catalyzed Meerwein-Ponndorf-Verley reduction to provide the equatorial alcohol 20 in excellent yield and stereoselectivity (de = 97%). Control experiments indicate that this surprisingly stereoselective reaction operates under kinetic control and that the observed stereochemical outcome may be the result of coordination of the reactive reducing agent to the axial spiroketal oxygen. Conversion of 20 to triol 4 afforded material that is identical with the rutamycin degradation product in all respects. These results establish that the absolute stereochemistry of the rutamycins is as shown (2a,b).