(2S,3S,6R,11R)-3,11-Dimethyl-2-<<<(1,1-dimethylethyl)diphenylsilyl>oxy>methyl>-1,7-dioxaspiro<5.5>undecane | 153109-02-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3S,6R,11R)-3,11-Dimethyl-2-<<<(1,1-dimethylethyl)diphenylsilyl>oxy>methyl>-1,7-dioxaspiro<5.5>undecane
• 英文别名: tert-butyl-[[(2S,3S,6R,11R)-3,11-dimethyl-1,7-dioxaspiro[5.5]undecan-2-yl]methoxy]-diphenylsilane
• CAS: 153109-02-5
• 化学式: C₂₈H₄₀O₃Si
• 分子量: 452.709
• InChiKey: AVPLTCKGHQEQSS-WLSLLGPHSA-N

物化性质

• 沸点：
  503.5±36.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.52
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3S,6R,11R)-3,11-Dimethyl-2-<<<(1,1-dimethylethyl)diphenylsilyl>oxy>methyl>-1,7-dioxaspiro<5.5>undecane 在 bis(acetylacetonate)oxovanadium 、 palladium dichloride 吡啶 、 2,6-二甲基吡啶 、 三乙基硅烷 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 重铬酸吡啶 、 正丁基锂 、 samarium diiodide 、 草酰氯 、 三甲基溴硅烷 、 3 A molecular sieve 、 4 A molecular sieve 、 氢氟酸 、 四丁基氟化铵 、 水 、 氧气 、 三乙基硅基三氟甲磺酸酯 、 四氯化钛 、 四氯化锡 、 sodium hydride 、 三乙基硼氢化锂 、 potassium carbonate 、 戴斯-马丁氧化剂 、 溶剂黄146 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 copper(l) chloride 、 lithium bromide 、 锌 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 乙醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 、 苯 为溶剂， 反应 135.58h， 生成 互变霉素
  参考文献：
  名称：

  Total Synthesis of Tautomycin

  摘要：

  A convergent stereocontrolled synthesis of the antifungal antibiotic tautomycin, a potent protein phosphatases inhibitor, has been achieved first via key aldol coupling of two large subunits, a right-hand C-1-C-21 ketone and a left-hand aldehyde (left from C-22). The C-1-C-10 segment was synthesized through a remote stereochemical control process using a spiroketal template. After joining with the C-11-C-18 segment, the spiroketal moiety was selectively constructed. Then the right-hand C-1-C-21 ketone was synthesized via Roush asymmetric crotylboration. The left-hand aldehyde was prepared from a C-21-C-26 Segment and a dialkylmaleic anhydride segment. Completely stereoselective assemblage of the two subunits, the right-hand and the left-hand, was achieved by employing the Mukaiyama aldol reaction. Further functional group manipulations including desilylation, oxidation at C-2, and deprotection of tert-butyl ester with concomitant anhydride formation provided tautomycin which was identical with the natural product. As a preliminary study, derivatizations and degradation of the natural product were also examined to support the total synthesis.

  DOI：

  10.1021/jo00121a026
• 作为产物：
  描述：

  (tert-butyldiphenylsilanyloxy)acetaldehyde 在 sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 正丁基锂 、 三甲基溴硅烷 、 三丁基膦 、 Raney Ni (W-2) 、 双氧水 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 作用下， 以 吡啶 、 乙醇 、 二氯甲烷 为溶剂， 生成 (2S,3S,6R,11R)-3,11-Dimethyl-2-<<<(1,1-dimethylethyl)diphenylsilyl>oxy>methyl>-1,7-dioxaspiro<5.5>undecane
  参考文献：
  名称：

  Synthetic study on tautomycin. Stereocontrolled synthesis of C(1)C(18) fragment using a strategy of selective reduction of spiroketal

  摘要：

  A stereocontrolled synthesis of C(1)-C(18) fragment of tautomycin is accomplished employing asymmetric crotylboration, selective reduction of spiroketal, and addition of crotylstannane as the key steps.

  DOI：

  10.1016/s0040-4039(00)74091-3

文献信息

• Reductive opening of α-methylspiroketals
  作者：Masato Oikawa、Hideaki Oikawa、Akitami Ichihara

  DOI：10.1016/0040-4020(95)00288-j

  日期：1995.5

  5]undecane 4 and its three congeners 5, 6, and 7 (α-methylspiroketals), and their reductive ring opening using aluminum hydride or silane - Lewis acid system have been investigated. Each spiroketal was synthesized through stereocontrolled acetalization with 42 – 96% diastereomeric excess (de). The diisobutylaluminum hydride reduction of α-methylspiroketals proceeded via the tight oxocarbenium ion pair complex

  研究了5-甲基-1,7-二氧杂螺[5.5]十一烷4及其三个同类物5、6和7（α-甲基螺酮）的合成，以及使用氢化铝或硅烷-路易斯酸体系的还原性开环。每个螺酮都是通过立体控制缩醛化合成的，其中非对映体过量为42-96％（de）。α-甲基螺环金属的二异丁基氢化铝还原反应通过紧密的氧碳鎓离子对络合物进行，其中位于C（α）-甲基键相反位置的CO键被裂解，从而得到结构保留性为50-100的产物％de。
• Highly regio- and stereoselective reductions of spiroketals
  作者：Hideaki Oikawa、Masato Oikawa、Akitami Ichihara、Kimiko Kobayashi、Masakazu Uramoto

  DOI：10.1016/s0040-4039(00)73980-3

  日期：1993.8

  Highly regio- and stereoselective reductions of the spiroketals have been achieved by DIBAH and silane-Lewis acid. The key factors of these selectivities were attributed to steric hindrance of alpha-methyl group at spiroketal and to vicinal ether oxygens for bidentate chelation.
• Total Synthesis of Tautomycin
  作者：Masato Oikawa、Tohru Ueno、Hideaki Oikawa、Akitami Ichihara

  DOI：10.1021/jo00121a026

  日期：1995.8

  A convergent stereocontrolled synthesis of the antifungal antibiotic tautomycin, a potent protein phosphatases inhibitor, has been achieved first via key aldol coupling of two large subunits, a right-hand C-1-C-21 ketone and a left-hand aldehyde (left from C-22). The C-1-C-10 segment was synthesized through a remote stereochemical control process using a spiroketal template. After joining with the C-11-C-18 segment, the spiroketal moiety was selectively constructed. Then the right-hand C-1-C-21 ketone was synthesized via Roush asymmetric crotylboration. The left-hand aldehyde was prepared from a C-21-C-26 Segment and a dialkylmaleic anhydride segment. Completely stereoselective assemblage of the two subunits, the right-hand and the left-hand, was achieved by employing the Mukaiyama aldol reaction. Further functional group manipulations including desilylation, oxidation at C-2, and deprotection of tert-butyl ester with concomitant anhydride formation provided tautomycin which was identical with the natural product. As a preliminary study, derivatizations and degradation of the natural product were also examined to support the total synthesis.
• Synthetic study on tautomycin. Stereocontrolled synthesis of C(1)C(18) fragment using a strategy of selective reduction of spiroketal
  作者：Masato Oikawa、Hideaki Oikawa、Akitami Ichihara

  DOI：10.1016/s0040-4039(00)74091-3

  日期：1993.7

  A stereocontrolled synthesis of C(1)-C(18) fragment of tautomycin is accomplished employing asymmetric crotylboration, selective reduction of spiroketal, and addition of crotylstannane as the key steps.