2-((1R,2R,3R,4R)-2-acetoxy-4-formyl-3-(triisopropylsilyloxy)-cyclobutyl)ethyl pivalate | 1528747-24-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-((1R,2R,3R,4R)-2-acetoxy-4-formyl-3-(triisopropylsilyloxy)-cyclobutyl)ethyl pivalate
• CAS: 1528747-24-1
• 化学式: C₂₃H₄₂O₆Si
• 分子量: 442.668
• InChiKey: AIVGBVAZJIEENW-XRXFAXGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  30.0
• 可旋转键数：
  10.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  78.9
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  2-((1R,2R,3R,4R)-2-acetoxy-4-formyl-3-(triisopropylsilyloxy)-cyclobutyl)ethyl pivalate 在 四丙基高钌酸铵 、 四甲基乙二胺 、 (2-methylpropyl)lithium 、 碳酸氢钠 、 potassium carbonate 、 戴斯-马丁氧化剂 、 N-甲基吗啉氧化物 、 亚甲基三苯基膦烷 、 sodium iodide 、 tin(ll) chloride 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 环己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 47.17h， 生成 (S)-5-((E)-3-(4-((tert-butyldimethylsilyloxy)methyl)-5-((1R,2R,4R)-2-(2-hydroxyethyl)-3-methylene-4-(triisopropylsilyloxy)cyclobutyl)furan-2-yl)-2-methylallyl)-3-(phenylselanyl)dihydrofuran-2(3H)-one
  参考文献：
  名称：

  Studies of the Synthesis of Providencin: Construction and Assembly of Two Major Subunits

  摘要：

  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.

  DOI：

  10.1021/jo402485h
• 作为产物：
  描述：

  2-((1R,2R,3R,4R)-2-acetoxy-3-(triisopropylsilyloxy)-4-vinylcyclobutyl)ethyl pivalate 在 2,6-二甲基吡啶 、 sodium periodate 、 四氧化锇 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 2.0h， 以68%的产率得到2-((1R,2R,3R,4R)-2-acetoxy-4-formyl-3-(triisopropylsilyloxy)-cyclobutyl)ethyl pivalate
  参考文献：
  名称：

  Studies of the Synthesis of Providencin: Construction and Assembly of Two Major Subunits

  摘要：

  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.

  DOI：

  10.1021/jo402485h