2,3,5,6-d4-p-cresol | 2876-03-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 酚类
• 英文名称: 2,3,5,6-d4-p-cresol
• 英文别名: p-Cresol-d4；2,3,5,6-tetradeuterio-4-methylphenol
• CAS: 2876-03-1
• 化学式: C₇H₈O
• 分子量: 112.108
• InChiKey: IWDCLRJOBJJRNH-QFFDRWTDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,3,5,6-d4-p-cresol 在 硫酸 、 水 、 phenyliodine(III) diacetate 作用下， 反应 20.0h， 生成 4-methyl-4-(prop-2-yn-1-yloxy)cyclohexa-2,5-dien-1-one-3,5-d₂
  参考文献：
  名称：

  Tunable Arylative Cyclization of 1,6-Enynes Triggered by Rhodium(III)-Catalyzed C–H Activation

  摘要：

  Two tunable arylative cyclizations of cyclohexadienone-containing 1,6-enynes are reported via rhodium(III)-catalyzed C-H activation of O-substituted N-hydroxybenzamides. The use of different O substituents, i.e. O-Piv and O-Me, on the directing group allows the formation of either tetracyclic isoquinolones through an (c)-Michael addition process or hydrobenzofurans through a (N)Michael addition process. Mechanistic investigations of these two cascade reactions clearly indicated that the C-H bond cleavage process was involved in the turnover-limiting step. Furthermore, the cyclization products could be subjected to various transformations for elaborating the pharmaceutically and synthetically valuable potential. This is the first example of a rhodium(III)-catalyzed arylative cyclization reaction of 1,6-enynes, and the results extend the application realm of Cp*Rh-III-catalyzed C-H activation cascade reactions.

  DOI：

  10.1021/ja5072702
• 作为产物：
  描述：

  对甲酚 在 重水 、 氘代硫酸 作用下， 反应 20.0h， 生成 2,3,5,6-d4-p-cresol
  参考文献：
  名称：

  在C–H活化和Diels–Alder反应的背景下，催化剂控制的区域发散性炔烃插入：融合和桥接循环的合成

  摘要：

  讨论了铑（III）和钴（III）催化吲哚的CH活化以及与1,6-炔烃的偶联。在铑（III）催化下，炔烃的插入遵循2,1-区域选择性，随后发生I型分子内Diels-Alder反应（IMDA），从而得到[6,5]稠合的循环。当被钴（III）同源物催化时，优选炔烃的1,2-插入，然后是稀有的II型IMDA，从而导致桥连的[3,3,1]循环。炔烃插入的选择性主要通过催化剂的空间敏感性来调节。

  DOI：

  10.1002/anie.201704036

文献信息

• Catalyst-Controlled Regiodivergent Alkyne Insertion in the Context of C−H Activation and Diels-Alder Reactions: Synthesis of Fused and Bridged Cycles
  作者：Xukai Zhou、Yupeng Pan、Xingwei Li

  DOI：10.1002/anie.201704036

  日期：2017.7.3

  Rhodium(III)- and cobalt(III)-catalyzed C−H activation of indoles and coupling with 1,6-enynes is discussed. Under rhodium(III) catalysis, the alkyne insertion follows 2,1-regioselectivity with a subsequent type-I intramolecular Diels–Alder reaction (IMDA) to afford [6,5]-fused cycles. When catalyzed by the cobalt(III) congener, 1,2-insertion of the alkyne is preferred, and followed by a rare type-II

  讨论了铑（III）和钴（III）催化吲哚的CH活化以及与1,6-炔烃的偶联。在铑（III）催化下，炔烃的插入遵循2,1-区域选择性，随后发生I型分子内Diels-Alder反应（IMDA），从而得到[6,5]稠合的循环。当被钴（III）同源物催化时，优选炔烃的1,2-插入，然后是稀有的II型IMDA，从而导致桥连的[3,3,1]循环。炔烃插入的选择性主要通过催化剂的空间敏感性来调节。
• Active site dynamics of toluene hydroxylation by cytochrome P-450
  作者：Robert P. Hanzlik、Kah Hiing John Ling

  DOI：10.1021/jo00300a010

  日期：1990.6
• Tunable Arylative Cyclization of 1,6-Enynes Triggered by Rhodium(III)-Catalyzed C–H Activation
  作者：Yuki Fukui、Ping Liu、Qiang Liu、Zhi-Tao He、Nuo-Yi Wu、Ping Tian、Guo-Qiang Lin

  DOI：10.1021/ja5072702

  日期：2014.11.5

  Two tunable arylative cyclizations of cyclohexadienone-containing 1,6-enynes are reported via rhodium(III)-catalyzed C-H activation of O-substituted N-hydroxybenzamides. The use of different O substituents, i.e. O-Piv and O-Me, on the directing group allows the formation of either tetracyclic isoquinolones through an (c)-Michael addition process or hydrobenzofurans through a (N)Michael addition process. Mechanistic investigations of these two cascade reactions clearly indicated that the C-H bond cleavage process was involved in the turnover-limiting step. Furthermore, the cyclization products could be subjected to various transformations for elaborating the pharmaceutically and synthetically valuable potential. This is the first example of a rhodium(III)-catalyzed arylative cyclization reaction of 1,6-enynes, and the results extend the application realm of Cp*Rh-III-catalyzed C-H activation cascade reactions.
• Enantioselective Kinetic Resolution/Desymmetrization of <i>Para</i> ‐Quinols: A Case Study in Boronic‐Acid‐Directed Phosphoric Acid Catalysis
  作者：Banruo Huang、Ying He、Mark D. Levin、Jaime A. S. Coelho、Robert G. Bergman、F. Dean Toste

  DOI：10.1002/adsc.201900816

  日期：2020.1.23

  A chiral phosphoric acid‐catalyzed kinetic resolution and desymmetrization of para‐quinols operating via oxa‐Michael addition was developed and subsequently subjected to mechanistic study. Good to excellent s‐factors/enantioselectivities were obtained over a broad range of substrates. Kinetic studies were performed, and DFT studies favor a hydrogen bonding activation mode. The mechanistic studies provide

  开发了一种通过手性磷酸催化的对羟基苯醌的动力学拆分和不对称化反应，并通过机理研究。在广泛的底物上均获得了良好至优异的S因子/对映选择性。进行了动力学研究，DFT研究倾向于氢键活化模式。机理研究为以前报道的涉及手性磷酸酯催化剂与硼酸结合的手性阴离子相转移反应提供了见识。