methyl 2,3,4-tri-O-benzyl-6,7,8-trideoxy-8-tributylstannyl-oct-6-eno-α-D-manno-1,5-pyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4-tri-O-benzyl-6,7,8-trideoxy-8-tributylstannyl-oct-6-eno-α-D-manno-1,5-pyranoside
• 化学式: C₄₂H₆₀O₅Sn
• 分子量: 763.645
• InChiKey: PQDAKVNRTBHMJC-YWFWTTMKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.52
• 重原子数：
  48
• 可旋转键数：
  22
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  46.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 2,3,4-tri-O-benzyl-6,7,8-trideoxy-8-tributylstannyl-oct-6-eno-α-D-manno-1,5-pyranoside 在 sodium tetrahydroborate 、 sodium periodate 、 三氟化硼乙醚 、 氟化氢吡啶 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 4.0h， 生成 methyl 2,3,4-tri-O-benzyl-6-deoxy-6-vinyl-α-D-manno-L-glycero-heptoside
  参考文献：
  名称：

  糖烯丙基锡与醛的反应。呋喃糖和吡喃糖有机金属衍生物之间的反应性有显着差异

  摘要：

  研究了单糖的有机金属衍生物与BF 3 ·OEt 2催化的醛类的反应。注意到吡喃硅烷基和呋喃基硅烷基烯丙基锡之间的反应性有显着差异。前者容易与醛反应，从而提供具有非常高的立体选择性的高级碳糖的前体，而后者在与醛反应之前进行了重排，消除了苯乙烯基部分。

  DOI：

  10.1016/s0957-4166(01)00331-7
• 作为产物：
  描述：

  正丁基锂 、 三正丁基氢锡 、 methyl 2,3,4-tri-O-benzyl-6,7,8-trideoxy-8-chloro-oct-6(E)-eno-α-D-manno-1,5-pyranoside 在 CuCN 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.5h， 以16%的产率得到methyl 2,3,4-tri-O-benzyl-6,7,8-trideoxy-6-butyl-oct-7-eno-α-D-manno-1,5-pyranoside
  参考文献：
  名称：

  仲糖烯丙基锡衍生物的合成及热稳定性

  摘要：

  与三糖烯丙基甲磺酸酯的反应Ñ -butyltin铜酸盐，得到初级和次级烯丙基锡衍生物：SUG-CHCH-CH 2 SnBu 3和SUG-CH（SnBu 3）-CHCH 2与后者者为主。S N 2'的添加几乎专门导致了一个在新创建的立体异构中心具有S构型的异构体。仅形成痕量的相反的R异构体。二级烯丙基锡的两种立体异构体均在高温（140°C）下分解，同时消除了锡部分并打开了糖环。主小号异构体给出dienoaldehyde CH 2 CH-CHCH - [（CHOR）3 ] -CHO，内部双键具有顺式几何构型。次要的R异构体在相同条件下提供反式二烯醛。这些结果有力地表明了仲糖烯丙基锡衍生物的热分解的协同作用（E2）机理。

  DOI：

  10.1016/s0957-4166(03)00312-4

文献信息

• Stability of regioisomeric sugar allyltins. Cleavage of the carbon oxygen bond under radical conditions
  作者：Sławomir Jarosz、Katarzyna Szewczyk

  DOI：10.1016/s0040-4039(01)00239-8

  日期：2001.4

  Secondary sugar allyltin derivatives [Sug-CH(SnBu3)-CH=CH2] decompose at high temperature (140 degreesC) with elimination of the tin moiety and opening of the sugar ring. The cis-dienoaldehydes thus formed react with Ph3P=CH-CO2Me to afford the corresponding trienes, which spontaneously undergo stereoselective intramolecular [4+2] cycloaddition to optically pure, highly oxygenated bicyclo[4.3.0]nonene derivatives. Primary sugar allyltins [Sug-CH=CHCH2-SnBu3] are thermally stable and do not decompose up to 170 degreesC. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Synthesis of highly oxygenated enantiomerically pure cis-bicyclo[4.3.0]nonanes from secondary sugar allyltin derivatives
  作者：Sławomir Jarosz、Katarzyna Szewczyk、Anna Zawisza

  DOI：10.1016/s0957-4166(03)00310-0

  日期：2003.6

  Secondary sugar allyltin derivatives of the D-series: Sug-CH(SnBu3)-CH=CH2 (obtained in an S(N)2' reaction of the corresponding primary allylic mesylates with 'Bu3SnCu') with the S-configuration at the stereogenic center bearing the -SnBu3 group decompose at 140degreesC to dienoaldehydes: CH2=CH-CH=CH-[(CHOR)(3)]-CHO with the cis geometry across the internal double bond. Such aldehydes react with the stabilized Wittig reagents to afford trienes, cyclization of which provides highly oxygenated enantiomerically pure cis-bicyclo[4.3.0]nonenes. This methodology is complementary to that recently proposed by us leading to such bicyclic systems, but with the trans junction between the five- and six-membered rings. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Joarosz, Slawomir; Szewczyk, Katarzyna, Tetrahedron, <hi>2001</hi>, vol. 57, # 35, p. 7548 - 7556
  作者：Joarosz, Slawomir、Szewczyk, Katarzyna

  DOI：——

  日期：——
• Reaction of sugar allyltins with aldehydes. A remarkable difference in reactivity between furanose and pyranose organometallic derivatives
  作者：Sławomir Jarosz、Stanisław Skóra、Katarzyna Szewczyk、Zbigniew Ciunik

  DOI：10.1016/s0957-4166(01)00331-7

  日期：2001.7

  The reaction of organometallic derivatives of monosaccharides with aldehydes catalyzed with BF3·OEt2 was studied. A significant difference in reactivity between the pyranosidic and furanosidic allyltins was noted. The former reacted readily with aldehydes affording precursors of higher carbon sugars with very high stereoselectivity, while the latter underwent rearrangement with elimination of the stannyl

  研究了单糖的有机金属衍生物与BF 3 ·OEt 2催化的醛类的反应。注意到吡喃硅烷基和呋喃基硅烷基烯丙基锡之间的反应性有显着差异。前者容易与醛反应，从而提供具有非常高的立体选择性的高级碳糖的前体，而后者在与醛反应之前进行了重排，消除了苯乙烯基部分。
• Synthesis and thermal stability of secondary sugar allyltin derivatives
  作者：Sławomir Jarosz、Katarzyna Szewczyk、Anna Zawisza

  DOI：10.1016/s0957-4166(03)00312-4

  日期：2003.6

  Reaction of sugar allylic mesylates with tri-n-butyltin cuprate affords the primary and secondary allyltin derivatives: Sug-CHCH-CH2SnBu3 and Sug-CH(SnBu3)-CHCH2 with the latter predominating. The SN2′ addition led almost exclusively to one isomer with the S configuration at the newly created stereogenic center. Only traces of the opposite R isomer were formed. Both stereoisomers of secondary allyltins

  与三糖烯丙基甲磺酸酯的反应Ñ -butyltin铜酸盐，得到初级和次级烯丙基锡衍生物：SUG-CHCH-CH 2 SnBu 3和SUG-CH（SnBu 3）-CHCH 2与后者者为主。S N 2'的添加几乎专门导致了一个在新创建的立体异构中心具有S构型的异构体。仅形成痕量的相反的R异构体。二级烯丙基锡的两种立体异构体均在高温（140°C）下分解，同时消除了锡部分并打开了糖环。主小号异构体给出dienoaldehyde CH 2 CH-CHCH - [（CHOR）3 ] -CHO，内部双键具有顺式几何构型。次要的R异构体在相同条件下提供反式二烯醛。这些结果有力地表明了仲糖烯丙基锡衍生物的热分解的协同作用（E2）机理。