甲磺酸,三氟-,6-羰基-1-环己烯-1-基酯 | 122948-46-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 中文名称: 甲磺酸,三氟-,6-羰基-1-环己烯-1-基酯
• 英文名称: 6-oxocyclohex-1-en-1-yl trifluoromethanesulfonate
• 英文别名: 2-triflyloxy-2-cyclohexenone；(6-oxocyclohexen-1-yl) trifluoromethanesulfonate
• CAS: 122948-46-3
• 化学式: C₇H₇F₃O₄S
• 分子量: 244.191
• InChiKey: DPPZSOXYROEJKQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  甲磺酸,三氟-,6-羰基-1-环己烯-1-基酯 在 sodium tetrahydroborate 、 cerium(III) chloride heptahydrate 、 四丁基氟化铵 、 copper(l) cyanide 、 三甲胺盐酸盐 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 甲苯 为溶剂， 反应 4.66h， 生成 2-phenyl-4,5,6,7-tetrahydro-1H-indole
  参考文献：
  名称：

  1,2-环己二烯与1,3-偶极子的有效捕集

  摘要：

  1,2-环己二烯是瞬态中间体，会经历快速二聚作用并被活化的烯烃和杂原子亲核试剂进行分子间捕获。氟介导的脱甲硅烷基消除容易获得的6-甲硅烷基环己烯-1-三氟甲磺酸酯可产生温和，化学选择性和官能团耐受的环丙二烯中间体，这些中间体可通过稳定的1,3-偶极子进行有效的捕集反应。反应在区域和非对映异构体选择性高的情况下进行。环状烯与叠氮化物的反应伴随着二氮的容易损失，取决于所使用的叠氮化物，导致四氢吲哚或多环氮丙啶的形成。

  DOI：

  10.1002/chem.201602201
• 作为产物：
  描述：

  三氟甲磺酸酐 、 1,2-环己二酮 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以91%的产率得到甲磺酸,三氟-,6-羰基-1-环己烯-1-基酯
  参考文献：
  名称：

  Chemoselective synthesis of allyltrimethylsilanes by cross-coupling of vinyl triflates with tris((trimethylsilyl)methyl)aluminum catalyzed by palladium(0)

  摘要：

  DOI：

  10.1021/ja00203a066

文献信息

• Rhodium-Catalyzed Tandem Cyclopropanation/Cope Rearrangement of 4-Alkenyl-1-sulfonyl-1,2,3-triazoles with Dienes
  作者：Brendan T. Parr、Huw M. L. Davies

  DOI：10.1002/anie.201304310

  日期：2013.9.16

  Take your pick…︁ A practical method for the synthesis of structurally diverse rhodium vinylcarbenes from stable 1‐sulfonyl‐1,2,3‐triazole precursors has been developed. The reaction is general for a broad range of 4‐alkenyl triazoles and dienes, enabling the stereoselective synthesis of a variety of polycyclic imines, which are readily converted into amines or aldehydes in a one‐pot process.

  请选择……pick已开发出一种由稳定的1-磺酰基-1,2,3-三唑前体合成结构多样的铑乙烯基卡宾的实用方法。该反应通常适用于范围广泛的4-链烯基三唑和二烯，可实现多种多环亚胺的立体选择性合成，这些多环亚胺可在一锅法中轻松转化为胺或醛。
• Enantioselective Palladium-Catalyzed Dearomative Cyclization for the Efficient Synthesis of Terpenes and Steroids
  作者：Kang Du、Pan Guo、Yuan Chen、Zhen Cao、Zheng Wang、Wenjun Tang

  DOI：10.1002/anie.201411817

  日期：2015.3.2

  efficient construction of a series of chiral phenanthrenone derivatives bearing an all‐carbon quaternary center. The effectiveness of this method in the synthesis of terpenes and steroids was demonstrated by a highly efficient synthesis of a kaurene intermediate, the facile construction of the skeleton of the anabolic steroid boldenone, and the enantioselective total synthesis of the antimicrobial diterpene

  为了有效构建一系列带有全碳四元中心的手性菲咯酮衍生物，开发了一种新颖的对映选择性钯催化的脱芳香环化反应。该方法在萜烯和类固醇合成中的有效性通过高效合成天竺葵中间体，合成代谢类固醇马来烯酮骨架的简便构建以及抗菌二萜天然产物（-）的对映选择性全合成得到了证明。雌二醇。
• Strictly regio-controlled method for α-alkenylation of cyclic ketones via palladium-catalyzed cross coupling
  作者：Ei-ichi Negishi、Zbyslaw R. Owczarczyk、Douglas R. Swanson

  DOI：10.1016/0040-4039(91)80010-4

  日期：1991.1

  Cyclic α-iodoenones and α-triflyloxyenones, but not α-bromoenones, smoothly react with alkenylzinc and related derivatives in the presence of a catalytic amount of a palladium-phosphine complex, such as Pd(PPh3)4 or Cl2Pd(PPh3)2 treated with n-BuLi (2 equiv), to give α-alkenylenones which can be conjugately reduced to the corresponding α-alkenyl ketones with complete retention of both enone regiochemistry

  在催化量的钯-膦配合物（例如Pd（PPh 3）4或Cl 2 Pd（PPh ）的存在下，环状α-碘烯和α-三氟乙酮，而不是α-溴烯，与烯基锌和相关衍生物平稳反应3）2用正丁基锂（2当量）处理，得到的α-烯基烯酮可以共轭还原为相应的α-烯基酮，同时完全保留烯酮的区域化学和烯基立体化学。
• Molecular Oxygen as a Redox Catalyst in Intramolecular Photocycloadditions of Coumarins
  作者：Darius Paul Kranz、Axel Georg Griesbeck、Ronald Alle、Raul Perez-Ruiz、Jörg Martin Neudörfl、Klaus Meerholz、Hans-Günther Schmalz

  DOI：10.1002/anie.201201222

  日期：2012.6.11

  Oxygen as a catalyst! While oxygen is usually excluded in nonoxidative photochemical reactions, the photocycloaddition of 3‐(alk‐4‐en‐1‐yl)‐substituted coumarins greatly benefits from the presence of O2, which was shown to act as a redox catalyst, preferentially in combination with the common antioxidant 3,5‐di‐tert‐butyl‐4‐hydroxytoluene (BHT).

  氧气作为催化剂！尽管在非氧化性光化学反应中通常会排除氧气，但3-（alk-4-en-1-基）取代的香豆素的光环加成反应会极大地受益于O 2的存在，O 2被证明是一种氧化还原催化剂，优先用于与常见的抗氧化剂3,5-二叔丁基-4-羟基甲苯（BHT）结合使用。
• Palladium-catalyzed coupling of arylstannanes with organic sulfonates: a comprehensive study
  作者：Vittorio Farina、Bala Krishnan、Daniel R. Marshall、Gregory P. Roth

  DOI：10.1021/jo00072a028

  日期：1993.9

  The effect of ligands and lithium chloride on the rates of the palladium catalyzed coupling between organic triflates and arylstannanes was studied. The dependence of the rate on the ligand is similar to the one previously reported for the coupling of vinylstannanes, but in the present case triphenylarsine is shown to be superior to both triphenylphosphine and tri(2-furyl)phosphine. The effect of added chloride is complex and varies depending on solvent and ligand used. Ortho-substituted arylstannanes tend to transfer alkyl moieties to a substantial extent , and therefore rates and efficiencies of aryl vs alkyl transfer were quantitated. When ortho substituents that are potentially coordinating to tin are used, no rate acceleration in the alkyl transfer process was observed, which is in contrast with two recently reported studies that suggest nucleophilic assistance at tin to be important in the transmetalation step. An important side reaction in the coupling of poorly reactive vinyltriflates and most aryltriflates is the Pd-induced homocoupling of the stannane to form biaryls. The experimental factors that control this process were evaluated.