(4aS,6R,7S,9aR)-7-(tert-Butyldimethylsiloxy)-6-vinyl-2,3,4,4a,8,9-hexahydropyrano<3,2-b>oxepane | 159293-03-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: (4aS,6R,7S,9aR)-7-(tert-Butyldimethylsiloxy)-6-vinyl-2,3,4,4a,8,9-hexahydropyrano<3,2-b>oxepane
• 英文别名: [(4aS,6R,7S,9aR)-6-ethenyl-3,4,4a,6,7,8,9,9a-octahydro-2H-pyrano[3,2-b]oxepin-7-yl]oxy-tert-butyl-dimethylsilane
• CAS: 159293-03-5
• 化学式: C₁₇H₃₂O₃Si
• 分子量: 312.525
• InChiKey: SSZRBKZLKPLWER-WCVJEAGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.29
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  (4aS,6R,7S,9aR)-7-(tert-Butyldimethylsiloxy)-6-vinyl-2,3,4,4a,8,9-hexahydropyrano<3,2-b>oxepane 在 咪唑 、 9-borabicyclo[3.3.1]nonane dimer 、 dimethyl sulfide borane 、 camphor-10-sulfonic acid 、 potassium tert-butylate 、 四丁基氟化铵 、 碘 、 二异丁基氢化铝 、 臭氧 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 苯 为溶剂， 反应 50.91h， 生成 (2S,3R,5S,6R)-5-Benzyloxy-6-benzyloxymethyl-2-[(4aS,6R,7S,9aR)-7-(4-methoxy-benzyloxy)-octahydro-1,5-dioxa-benzocyclohepten-6-ylmethyl]-tetrahydro-pyran-3-ol
  参考文献：
  名称：

  Gymnocin-A 的收敛全合成和合成类似物的评价

  摘要：

  Gynocin-A (1) 的首次全合成已经完成，这是一种从臭名昭著的赤潮甲藻中分离的细胞毒性多环醚，Karenia mikimotoi，已经完成。合成在很大程度上依赖于 Suzuki-Miyaura 基于交叉偶联的方法来组装十四环聚醚骨架。GHI (5) 和 KLMN (6) 环的收敛联合，这两者都是由一个共同的中间体 7 制备的，随后 J 环的环闭合提供了 GHIJKLMN 环。ABCD 和 FGHIJKLMN 环片段（分别为 3 和 4）之间的关键耦合和 C17 羟基的立体选择性安装，随后 E 环的环化产生了十四环聚醚骨架 2。最后，2-甲基的掺入-2-丁烯醛侧链完成了金霉素-A的全合成。合成的收敛性质使用了三个具有可比复杂性的片段，非常适合制备金霉素 A 的各种结构类似物，以探索构效关系。还提供了几种合成类似物的初步构效关系研究结果。

  DOI：

  10.1021/ja042686r
• 作为产物：
  描述：

  (2R,3S)-tert-butyl(2-iodomethyltetrahydropyran-3-yloxy)dimethylsilane 在 四氧化锇 偶氮二异丁腈 、 camphor-10-sulfonic acid 、 四丁基氟化铵 、 水 、 sodium hydride 、 N-甲基吗啉氧化物 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 丙酮 、 苯 为溶剂， 反应 16.08h， 生成 (4aS,6R,7S,9aR)-7-(tert-Butyldimethylsiloxy)-6-vinyl-2,3,4,4a,8,9-hexahydropyrano<3,2-b>oxepane
  参考文献：
  名称：

  Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations

  摘要：

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.

  DOI：

  10.1021/jo00089a034

文献信息

• Stereocontrolled intramolecular cyclization of ω-tributylstannyl ether aldehydes. synthesis of the 6·7·7·6 ring system of polycyclic ethers
  作者：Yoshinori Yamamoto、Jun-ichi Yamada、Isao Kadota

  DOI：10.1016/0040-4039(91)85042-4

  日期：1991.11

  γ-oxo-substituted allylic tin (1) having an aldehyde group at the terminus of the carbon chain proceeded in a stereocontrolled manner to give the 7-membered β-hydroxy cyclic ether (2a) with high diastereoselectivity. This method was applied for the synthesis of the 6·7·7·6 ring system (3a).

  BF 3 .OEt 2介导的在碳链末端具有醛基的γ-氧代取代的烯丙基锡（1）的分子内环化以立体控制的方式进行，得到了7元的β-羟基环醚（2a）高非对映选择性。该方法被用于6·7·7·6环系统（3a）的合成。
• Convergent Total Synthesis of Gymnocin-A and Evaluation of Synthetic Analogues
  作者：Chihiro Tsukano、Makoto Ebine、Makoto Sasaki

  DOI：10.1021/ja042686r

  日期：2005.3.1

  subsequent ring closure of the J ring delivered the GHIJKLMN ring. The crucial coupling between the ABCD and FGHIJKLMN ring fragments (3 and 4, respectively) and stereoselective installation of the C17 hydroxyl group, followed by cyclization of the E ring gave rise to the tetradecacyclic polyether skeleton 2. Finally, incorporation of the 2-methyl-2-butenal side chain completed the total synthesis of gymnocin-A

  Gynocin-A (1) 的首次全合成已经完成，这是一种从臭名昭著的赤潮甲藻中分离的细胞毒性多环醚，Karenia mikimotoi，已经完成。合成在很大程度上依赖于 Suzuki-Miyaura 基于交叉偶联的方法来组装十四环聚醚骨架。GHI (5) 和 KLMN (6) 环的收敛联合，这两者都是由一个共同的中间体 7 制备的，随后 J 环的环闭合提供了 GHIJKLMN 环。ABCD 和 FGHIJKLMN 环片段（分别为 3 和 4）之间的关键耦合和 C17 羟基的立体选择性安装，随后 E 环的环化产生了十四环聚醚骨架 2。最后，2-甲基的掺入-2-丁烯醛侧链完成了金霉素-A的全合成。合成的收敛性质使用了三个具有可比复杂性的片段，非常适合制备金霉素 A 的各种结构类似物，以探索构效关系。还提供了几种合成类似物的初步构效关系研究结果。
• Simple Designs for the Construction of Complex trans-Fused Polyether Toxin Frameworks. A Linear Strategy Based on Entropically Favored Oxirane Ring Enlargement in Epoxycycloalkenes Followed by Carbon-Carbon or Carbon-Oxygen Bond-Forming Cyclizations
  作者：Eleuterio Alvarez、Maria T. Diaz、Ricardo Perez、Jose L. Ravelo、Alicia Regueiro、Jose A. Vera、Dacil Zurita、Julio D. Martin

  DOI：10.1021/jo00089a034

  日期：1994.5

  A successful design for the construction of trans-fused medium-size cyclic ethers is described. The key features of the synthesis are as follows: (i) intramolecular oxirane ring expansion in cycloalkenes to give bridged oxabicyclic systems and (ii) linear, one- or two-directional synthetic operations which generate external oxocycles in single reaction steps. The general approach involves the intramolecular addition of a stable gamma-alkoxy-substituted allylstannane to an aldehyde carbonyl group, and the entire reaction is conducted in a one-pot process which includes the following: (i) vic-diol fragmentation from the bridged oxabicyclic precursor and (ii) Lewis acid-induced cyclization of the resulting aldehyde-allylic tin system. While the present strategy was mostly developed around racemic models, the potential for adoption of;enantioselective features is immediate. The versatility, scope, limitations, and potential applications of the present technology are discussed in detail.