(R)-4-methylcycloheptanone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-4-methylcycloheptanone
• 英文别名: (S)-4-methylcycloheptanone；(4S)-4-methylcycloheptan-1-one
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: WXVNSHRGPVHBPD-ZETCQYMHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (R)-4-methylcyclohexylidenemethyl(3-trifluoromethylphenyl)iodonium tetrafluoroborate 在 2,2,2-三氟乙醇 作用下， 反应 7.0h， 生成 (4R)-4-甲基环庚烷-1-酮 、 (R)-4-methylcycloheptanone
  参考文献：
  名称：

  4-甲基环己叉基甲基碘盐的溶剂化：手性探针法合成伯乙烯基阳离子中间体。

  摘要：

  制备了光学活性的4-甲基环己叉基甲基（芳基）碘化四氟硼酸酯（1.BF（4）（-）），并在60℃下于各种溶剂中进行了溶剂分解。主要产物是在无缓冲溶剂中伴随有碘芳烃的旋光性4-甲基环庚酮（或其烯醇衍生物）。重排的产物始终保持起始1的光学纯度。其立体化学符合一种机制，该机制涉及通过sigma键参与核反应堆的离开而进行重排，然后捕获所得的手性5-甲基环庚-1-烯阳离子亲核溶剂。也就是说，在反应过程中不涉及非手性伯乙烯基阳离子。还可以在未缓冲的甲醇，乙醇和乙酸中以小部分获得未重排的取代产物，但不是在三氟乙醇或六氟-2-丙醇中：甲醇分解的甲氧基产物在很大程度上消旋，但乙酰化产物主要是通过保留构型获得的。1与溴化物，乙酸盐和三氟乙酸盐在氯仿中的反应在不同的转化度下产生未排列的取代产物。这些未重排的产物被认为是通过直接亲核取代形成的。在甲醇中添加碱（如乙酸钠）会导致外消旋的完全重排的甲氧基产物重新排列，这

  DOI：

  10.1021/jo020398c

文献信息

• Cycloheptyne Intermediate in the Reaction of Chiral Cyclohexylidenemethyliodonium Salt with Sulfonates
  作者：Morifumi Fujita、Yuichi Sakanishi、Masayoshi Nishii、Tadashi Okuyama

  DOI：10.1021/jo0203995

  日期：2002.11.1

  Reactions of (R)-4-methyleyclohexylidenemethyl(phenyl)iodonium salt and its 3-trifluoromethylphenyl and 4-methoxyphenyl derivatives (1) with tetrabutylammonium mesylate and triflate were carried out in chloroform at 60 degreesC. The products include (S)-4-methylcyclohexylidenemethyl sulfonate (2) and (R)-5-methylcyclohept-1-enyl sulfonate (3) as well as iodoarene. Reactions of (S)-1 were confirmed to provide the counterpart results. The rearranged triflate (R)-3Tf formed in the reaction with triflate maintains mostly the ee (enantiomeric excess) of (R)-1, while the ee of the mesylate product 3Ms is largely lost. The C-13-labeling at the exocyclic position of 1 results in the isotopic scrambling of C-1 and C-2 of 3Ms in the mesylate reaction. The degree of the scrambling agrees well with that of the loss of ee of (R)-3Ms obtained from (R)-1, implying that the racemization is not due to the intermediate formation of achiral, primary 4-methylcyclohexylidenemethyl cation. Reaction of 1 with mesylate in the presence of CH3OD provided the 3Ms deuterated at the 2-position. When tetraphenylcyclopentadienone was added to the mesylate reaction system, the adduct of the 4-methylcycloheptyne intermediate was obtained in 24% yield, but the normal products 2Ms and 3Ms were still formed. The 3Ms obtained here in a low yield maintains the high ee of 1. These results indicate that the cycloheptyne is an intermediate responsible for the formation of racemic product 3Ms in the mesylate reaction. It is also concluded that the unrearranged products 2 are formed via the competitive pathways of in-plane and out-of-plane S(N)2 reactions.
• Photosolvolysis of optically active 4-methyl-cyclohexylidenemethyl(aryl)iodonium tetrafluoroborate
  作者：Morifumi Fujita、Machiko Furutani、Tadashi Okuyama

  DOI：10.1016/s0040-4039(02)02057-9

  日期：2002.11

  The title reaction gives largely racemized 4-methylcycloheptanone, but the enantiomeric product in slight excess has a different form depending on the leaving group, ArI, of the iodonium salt. The results indicate that the photosolvolysis does not proceed via a completely achiral state. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Solvolysis of 4-Methylcyclohexylidenemethyliodonium Salt:  Chirality Probe Approach to a Primary Vinyl Cation Intermediate
  作者：Morifumi Fujita、Yuichi Sakanishi、Masayoshi Nishii、Hiroshi Yamataka、Tadashi Okuyama

  DOI：10.1021/jo020398c

  日期：2002.11.1

  also obtained in a minor fraction in unbuffered methanol, ethanol, and acetic acid, but not in trifluoroethanol or hexafluoro-2-propanol: the methoxy product from methanolysis is largely racemized, but the acetolysis product is obtained mainly via retention of configuration. Reactions of 1 with bromide, acetate, and trifluoroacetate in chloroform give unrearranged substitution products in different

  制备了光学活性的4-甲基环己叉基甲基（芳基）碘化四氟硼酸酯（1.BF（4）（-）），并在60℃下于各种溶剂中进行了溶剂分解。主要产物是在无缓冲溶剂中伴随有碘芳烃的旋光性4-甲基环庚酮（或其烯醇衍生物）。重排的产物始终保持起始1的光学纯度。其立体化学符合一种机制，该机制涉及通过sigma键参与核反应堆的离开而进行重排，然后捕获所得的手性5-甲基环庚-1-烯阳离子亲核溶剂。也就是说，在反应过程中不涉及非手性伯乙烯基阳离子。还可以在未缓冲的甲醇，乙醇和乙酸中以小部分获得未重排的取代产物，但不是在三氟乙醇或六氟-2-丙醇中：甲醇分解的甲氧基产物在很大程度上消旋，但乙酰化产物主要是通过保留构型获得的。1与溴化物，乙酸盐和三氟乙酸盐在氯仿中的反应在不同的转化度下产生未排列的取代产物。这些未重排的产物被认为是通过直接亲核取代形成的。在甲醇中添加碱（如乙酸钠）会导致外消旋的完全重排的甲氧基产物重新排列，这