(2R)-2-Methyl-5-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-1-pentanol | 123595-52-8

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (2R)-2-Methyl-5-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-1-pentanol
• 英文别名: (R)-5-((tert-butyldiphenylsilyl)oxy)-2-methylpentan-1-ol；(2R)-5-[tert-butyl(diphenyl)silyl]oxy-2-methylpentan-1-ol
• CAS: 123595-52-8
• 化学式: C₂₂H₃₂O₂Si
• 分子量: 356.58
• InChiKey: FSURQKSRZPQKQC-LJQANCHMSA-N

物化性质

• 沸点：
  423.7±37.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.97
• 重原子数：
  25.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (2R)-2-Methyl-5-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-1-pentanol 在 bis(acetylacetonate)oxovanadium 、 palladium dichloride 吡啶 、 2,6-二甲基吡啶 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 sodium hydroxide 、 重铬酸吡啶 、 9-borabicyclo[3.3.1]nonane dimer 、 正丁基锂 、 samarium diiodide 、 草酰氯 、 三甲基溴硅烷 、 三丁基膦 、 3 A molecular sieve 、 4 A molecular sieve 、 三氟化硼乙醚 、 氢氟酸 、 四丁基氟化铵 、 水 、 双氧水 、 氧气 、 三乙基硅基三氟甲磺酸酯 、 四氯化钛 、 三乙基硼氢化锂 、 碳酸氢钠 、 potassium carbonate 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 三乙胺 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 、 copper(l) chloride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 152.58h， 生成 <2S,2(7E,1R,4S,5S,9S,10R),3S,6R,8S,8(3S),9R>-2-<4,10-Bis<(triethylsilyl)oxy>-9-methoxy-1,5,11-trimethyl-6-oxo-7-dodecenyl>-8-<4-<<(trifluoromethyl)sulfonyl>oxy>-3-methyl-4-pentenyl>-3,9-dimethyl-1,7-dioxaspiro<5.5>undecane
  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：

  Ethyl (4R)-5-(tetrahydropyran-2-yloxy)-4-methyl-2-pentenoate 在 palladium on activated charcoal 咪唑 、 lithium aluminium tetrahydride 、 氢气 、 对甲苯磺酸 作用下， 以 甲醇 、 乙醚 、 乙酸乙酯 、 N,N-二甲基甲酰胺 为溶剂， 反应 25.33h， 生成 (2R)-2-Methyl-5-<<(1,1-dimethylethyl)diphenylsilyl>oxy>-1-pentanol
  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

文献信息

• Total Synthesis of Strasseriolide A
  作者：Moinul Haque Sahana、Dhiman Saha、Rajib Kumar Goswami

  DOI：10.1021/acs.joc.2c01595

  日期：2022.9.2

  Stereoselective total synthesis of structurally intriguing antimalarial macrolide strasseriolide A has been accomplished by adopting a convergent approach. The salient features of this synthesis include Co(BH4)2-mediated selective reduction of conjugated olefin, Crimmins propionate aldol, Evans alkylation, intermolecular Horner–Wadsworth–Emmons olefination, Yamaguchi macrolactonization, and selective

  结构上有趣的抗疟疾大环内酯类strasseriolide A的立体选择性全合成已通过采用收敛方法完成。该合成的显着特征包括 Co(BH 4 ) 2介导的共轭烯烃选择性还原、Crimmins 丙酸醛醇、Evans 烷基化、分子间 Horner-Wadsworth-Emmons 烯化、Yamaguchi 大环内酯化和酯部分的选择性皂化。内酯功能。发现 strasseriolide A的13 C 1 H} NMR 数据对其溶液浓度非常敏感。
• Application of In Situ-Generated Rh-Bound Trimethylenemethane Variants to the Synthesis of 3,4-Fused Pyrroles
  作者：Erica E. Schultz、Richmond Sarpong

  DOI：10.1021/ja401380d

  日期：2013.3.27

  Rh-bound trimethylenemethane variants generated from the interaction of a Rh-carbenoid with an allene have been applied to the synthesis of substituted 3,4-fused pyrroles. The pyrrole products are useful starting points for the syntheses of various dipyrromethene ligands. Furthermore, the methodology has been applied to a synthesis of the natural product cycloprodigiosin, which demonstrates antitumor and immunosuppressor activity.
• 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.
• HANESSIAN, S.;THAVONEKHAM, B.;DEHOFF, B., J. ORG. CHEM., 54,(1989) N5, C. 5831-5833
  作者：HANESSIAN, S.、THAVONEKHAM, B.、DEHOFF, B.

  DOI：——

  日期：——