4,6,6-trimethyl-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: 4,6,6-trimethyl-oxepan-2-one
• 英文别名: (4S)-4,6,6-trimethyloxepan-2-one
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: OSKVFHONCZMKCM-SSDOTTSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.99
• 重原子数：
  11.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  3,3,5-三甲基环己酮 在 air 、 cyclohexanone monooxygenase 作用下， 反应 20.0h， 生成 4,6,6-trimethyl-oxepan-2-one 、 4,4,6-trimethyl-oxepan-2-one
  参考文献：
  名称：

  Crystal Structures of Cyclohexanone Monooxygenase Reveal Complex Domain Movements and a Sliding Cofactor

  摘要：

  Cyclohexanone monooxygenase (CHMO) is a flavoprotein that carries out the archetypical Baeyer-Villiger oxidation of a variety of cyclic ketones into lactones. Using NADPH and O-2 as cosubstrates, the enzyme inserts one atom of oxygen into the substrate in a complex catalytic mechanism that involves the formation of a flavin-peroxide and Criegee intermediate. We present here the atomic structures of CHMO from an environmental Rhodococcus strain bound with FAD and NADP(+) in two distinct states, to resolutions of 2.3 and 2.2 angstrom. The two conformations reveal domain shifts around multiple linkers and loop movements, involving conserved arginine 329 and tryptophan 492, which effect a translation of the nicotinamide resulting in a sliding cofactor. Consequently, the cofactor is ideally situated and subsequently repositioned during the catalytic cycle to first reduce the flavin and later stabilize formation of the Criegee intermediate. Concurrent movements of a loop adjacent to the active site demonstrate how this protein can effect large changes in the size and shape of the substrate binding pocket to accommodate a diverse range of substrates. Finally, the previously identified BVMO signature sequence is highlighted for its role in coordinating domain movements. Taken together, these structures provide mechanistic insights into CHMO-catalyzed Baeyer-Villiger oxidation.

  DOI：

  10.1021/ja9010578