3-(2,2,2-trifluoroacetyl)oxepan-2-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 3-(2,2,2-trifluoroacetyl)oxepan-2-one
• 英文别名: 3-(2,2,2-Trifluoroacetyl)oxepan-2-one
• 化学式: C₈H₉F₃O₃
• 分子量: 210.153
• InChiKey: PWFCGKLJALWQGZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3-(2,2,2-trifluoroacetyl)oxepan-2-one 在 o-nitrobenzenesulfonyl azide 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以1.28 g的产率得到3-diazooxepan-2-one
  参考文献：
  名称：

  Engineered Cytochrome c-Catalyzed Lactone-Carbene B–H Insertion

  摘要：

  先前的工作表明，一种血红素蛋白变体，Rhodothermus marinus细胞色素c（Rma cyt c），以高效率和选择性催化非生物碳硼-氢（B-H）键插入。在这里，我们研究了环状、内酯基碳烯与硼之间形成键的化学反应。通过定向进化，我们获得了一种Rma cyt c变体BORLAC，对于5-和6-成员内酯基碳烯的B-H插入显示出高选择性和高效率（最高达24,500次总转化率和97.1:2.9立体异构比）。该酶对于7-成员内酯基碳烯的活性较低。计算研究揭示了相对于5-和6-成员内酯基碳烯，7-成员内酯基碳烯中间体的几何构型高度扭曲。通过对细胞色素c的定向进化以及关键铁-碳烯中间体的计算表征，我们已经扩展了酶催化碳烯B-H插入的范围，以产生新的基于内酯的有机硼化合物。

  DOI：

  10.1055/s-0037-1611662
• 作为产物：
  描述：

  6-己内酯 、 alkaline earth salt of/the/ methylsulfuric acid 在 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 0.58h， 生成 3-(2,2,2-trifluoroacetyl)oxepan-2-one
  参考文献：
  名称：

  Deacylative Oxidation Strategy for the Preparation of α-Functionalized Carbonyls

  摘要：

  alpha-Alkoxylation and amination of carbonyl derivatives is made possible through a unique deacylative coupling reaction that proceeds via in situ Rh-carbene formation and subsequent heteroatom-H (X-H) insertion. Reactions perform optimally with five- and six-membered ring lactone and lactam derivatives using both alcohol and carbamate substrates as coupling partners. Substituted ethylbenzoyl acetate starting materials have also proven to be effective for this oxidative process, affording alpha-functionalized esters under particularly mild and operationally facile conditions.

  DOI：

  10.1021/ol040039z

文献信息

• Deacylative Oxidation Strategy for the Preparation of α-Functionalized Carbonyls
  作者：Benjamin H. Brodsky、J. Du Bois

  DOI：10.1021/ol040039z

  日期：2004.7.1

  alpha-Alkoxylation and amination of carbonyl derivatives is made possible through a unique deacylative coupling reaction that proceeds via in situ Rh-carbene formation and subsequent heteroatom-H (X-H) insertion. Reactions perform optimally with five- and six-membered ring lactone and lactam derivatives using both alcohol and carbamate substrates as coupling partners. Substituted ethylbenzoyl acetate starting materials have also proven to be effective for this oxidative process, affording alpha-functionalized esters under particularly mild and operationally facile conditions.
• Engineered Cytochrome c-Catalyzed Lactone-Carbene B–H Insertion
  作者：Kai Chen、Xiongyi Huang、Shuo-Qing Zhang、Andrew Zhou、S. B. Jennifer Kan、Xin Hong、Frances Arnold

  DOI：10.1055/s-0037-1611662

  日期：2019.3

  Previous work has demonstrated that variants of a heme protein, Rhodothermus marinus cytochrome c (Rma cyt c), catalyze abiological carbene boron–hydrogen (B–H) bond insertion with high efficiency and selectivity. Here we investigated this carbon–boron bond-forming chemistry with cyclic, lactone-based carbenes. Using directed evolution, we obtained a Rma cyt c variant BORLAC that shows high selectivity and efficiency for B–H insertion of 5- and 6-membered lactone carbenes (up to 24,500 total turnovers and 97.1:2.9 enantiomeric ratio). The enzyme shows low activity with a 7-membered lactone carbene. Computational studies revealed a highly twisted geometry of the 7-membered lactone carbene intermediate relative to 5- and 6-membered ones. Directed evolution of cytochrome c together with computational characterization of key iron-carbene intermediates has allowed us to expand the scope of enzymatic carbene B–H insertion to produce new lactone-based organoborons.

  先前的工作表明，一种血红素蛋白变体，Rhodothermus marinus细胞色素c（Rma cyt c），以高效率和选择性催化非生物碳硼-氢（B-H）键插入。在这里，我们研究了环状、内酯基碳烯与硼之间形成键的化学反应。通过定向进化，我们获得了一种Rma cyt c变体BORLAC，对于5-和6-成员内酯基碳烯的B-H插入显示出高选择性和高效率（最高达24,500次总转化率和97.1:2.9立体异构比）。该酶对于7-成员内酯基碳烯的活性较低。计算研究揭示了相对于5-和6-成员内酯基碳烯，7-成员内酯基碳烯中间体的几何构型高度扭曲。通过对细胞色素c的定向进化以及关键铁-碳烯中间体的计算表征，我们已经扩展了酶催化碳烯B-H插入的范围，以产生新的基于内酯的有机硼化合物。