tert-butyl((1R,2R,3R,4R)-2-(2-(4-methoxybenzyloxy)ethyl)-4-(triisopropylsilyloxy)-3-vinylcyclobutoxy)dimethylsilane | 1133094-82-2

• 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: tert-butyl((1R,2R,3R,4R)-2-(2-(4-methoxybenzyloxy)ethyl)-4-(triisopropylsilyloxy)-3-vinylcyclobutoxy)dimethylsilane
• CAS: 1133094-82-2
• 化学式: C₃₁H₅₆O₄Si₂
• 分子量: 548.954
• InChiKey: HGFCDXULDQIGGD-SKKKGAJSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.99
• 重原子数：
  37.0
• 可旋转键数：
  14.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  tert-butyl((1R,2R,3R,4R)-2-(2-(4-methoxybenzyloxy)ethyl)-4-(triisopropylsilyloxy)-3-vinylcyclobutoxy)dimethylsilane 在 氧气 、 copper(l) chloride 、 palladium dichloride 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 以77%的产率得到1-((1R,2R,3R,4R)-3-(tert-butyldimethylsilyloxy)-2-(2-(4-methoxybenzyloxy)ethyl)-4-(triisopropylsilyloxy)cyclobutyl)ethanone
  参考文献：
  名称：

  Synthesis of the Cyclobutylfuran Sector of Providencin via Zirconium-mediated Oxygen Abstraction from a Furanoside

  摘要：

  A portion of the macrocyclic cembrenoid diterpene providencin possessing conjoined cyclobutane and furancarboxylate units was synthesized from D-glucose using deoxygenative ring contraction methodology to construct the tetrasubstituted cyclobutane and a Knoevenagel condensation of glyceraldehyde to fabricate the trisubstituted furan.

  DOI：

  10.1021/ol900152p
• 作为产物：
  描述：

  (1R,2R,3R,4R)-2-(tert-butyldimethylsilyloxy)-3-(2-(4-methoxybenzyloxy)ethyl)-4-vinylcyclobutanol 、 三异丙基硅基三氟甲磺酸酯 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 15.0h， 以98%的产率得到tert-butyl((1R,2R,3R,4R)-2-(2-(4-methoxybenzyloxy)ethyl)-4-(triisopropylsilyloxy)-3-vinylcyclobutoxy)dimethylsilane
  参考文献：
  名称：

  Synthesis of the Cyclobutylfuran Sector of Providencin via Zirconium-mediated Oxygen Abstraction from a Furanoside

  摘要：

  A portion of the macrocyclic cembrenoid diterpene providencin possessing conjoined cyclobutane and furancarboxylate units was synthesized from D-glucose using deoxygenative ring contraction methodology to construct the tetrasubstituted cyclobutane and a Knoevenagel condensation of glyceraldehyde to fabricate the trisubstituted furan.

  DOI：

  10.1021/ol900152p

文献信息

• Studies of the Synthesis of Providencin: Construction and Assembly of Two Major Subunits
  作者：James D. White、Somnath Jana

  DOI：10.1021/jo402485h

  日期：2014.1.17

  The "northern" sector of the cembranoid diterpene providencin containing a tetrasubstituted cyclobutane was synthesized from the bis(acetonide) of D-glucose using dicyclopentadienylzirconium(0)-mediated oxygen abstraction from a furanose. Oxidative scission of the vinyl substituent of this cyclobutane gave an aldehyde, which was reacted with an alkynylstannane to provide an allenol. Cyclization of the derived allenone with silver nitrate led to a cyclobutylfuran comprising the northern subunit of providencin. The "southern" sector of the cembranoid skeleton containing a trisubstituted iodoalkene attached to an alpha-phenylselenyl-gamma-lactone was synthesized from (R)-glycidol. Negishi carbometalation-iodination established the (E)-iodoalkene, and addition of the lithio dianion of phenylselenoacetic acid to a tosylate generated the substituted lactone. The two sectors were joined via stannylation of the furan of the northern component followed by Stille cross-coupling of the furylstannane with the iodoalkene of the southern subunit. Linkage of the two segments was also made at C12-C13 of providencin using intermolecular aldol condensation of the enolate from the selenyl lactone of the southern portion with an acetaldehyde appendage on the cyclobutane of the northern sector. Closure of the providencin macrocycle from these conjoined subunits was unsuccessful.