trimethyloxosulfonium iodide

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: trimethyloxosulfonium iodide
• 英文别名: trimethylsulfoxonium iodide；(Trimethyl-lambda4-sulfanyl) hypoiodite；(trimethyl-λ4-sulfanyl) hypoiodite
• 化学式: C₃H₉IOS
• 分子量: 220.074
• InChiKey: GFBDAXZCIQNJEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  6
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  10.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trimethyloxosulfonium iodide 、 对甲氧基苯乙酮 在 sodium hydride 作用下， 以 四氢呋喃 、 mineral oil 为溶剂， 反应 49.0h， 以71%的产率得到2-(4-methoxyphenyl)-2-methyloxirane
  参考文献：
  名称：

  β-tert-Butyl aspartate as an organocatalyst for the asymmetric α-amination of α,α-disubstituted aldehydes

  摘要：

  The enantioselective alpha-amination reaction of alpha,alpha-disubstituted aldehydes can lead to a variety of enantioenriched amino aldehydes, amino alcohols, and amino acids. After screening a variety of amino acids and their derivatives, we identified a cheap, simple, commercially available aspartic acid derivative that can catalyze efficiently the reaction between alpha,alpha-disubstituted aldehydes and dialkyl azodicarboxylates. The reaction proceeds smoothly leading to the corresponding alpha-aminated adducts in moderate to quantitative yields and moderate to high enantioselectivities (up to 96% ee). Finally, the conversion of these adducts to alpha,alpha-disubstituted quaternary amino acids is also described. 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.04.103
• 作为试剂：
  描述：

  2-(3-Trimethylsilanyl-prop-2-ynylidene)-malonic acid diethyl ester 在 sodium hydride 、 trimethyloxosulfonium iodide 作用下， 以 二甲基亚砜 为溶剂， 以53 %的产率得到diethyl 2-((trimethylsilyl)ethynyl)cyclopropane-1,1-dicarboxylate
  参考文献：
  名称：

  金催化2-炔基氮杂环丁烷与醇的亲核开环反应

  摘要：

  描述了 2-炔基氮杂环丁烷和醇与金催化剂的反应。通过醇的金促进亲核攻击，然后氮杂环丁烷环的开环，合成了多种取代的δ-氨基-α,β-不饱和酮。

  DOI：

  10.1021/acs.joc.2c01325

文献信息

• Synthesis of α-Thiooximes by Addition of Thiols to N,N-Bis(oxy)-enamines: A Comparative Study of S-, N-, and O-Nucleo­philes in Michael Reaction with Nitrosoalkene Species
  作者：Alexey Sukhorukov、Yana Naumovich、Aleksandr Kokuev、Sema Ioffe

  DOI：10.1055/s-0036-1591973

  日期：2018.6

  Nucleophilic addition of thiols to N , N -bis(oxy)enamines (nitrosoalkene acetals) produce valuable α-thiooximes in a highly efficient manner. The reaction was found to be solvent-dependent, likely because of distinct mechanisms operating in nonpolar and basic solvents (involving either Bronsted acid or Lewis base catalysis). By performing a series of competition experiments, the relative reactivity

  硫醇与 N，N-双（氧）烯胺（亚硝基烯烃缩醛）的亲核加成以高效的方式产生有价值的 α-硫肟。发现该反应依赖于溶剂，可能是因为在非极性和碱性溶剂（涉及布朗斯台德酸或路易斯碱催化）中运行的不同机制。通过进行一系列竞争实验，首次测定了 S-、N-和 O-亲核试剂与 N、N-双（氧）烯胺反应的相对反应性。有趣的是，发现相对亲核性高度依赖于溶剂，这允许通过使用适当的介质对这些反应进行区域选择性控制。
• Syntheses of 1,2-distributed adamantanes
  作者：Ashraf N. Abdel-Sayed、Ludwig Bauer

  DOI：10.1016/s0040-4020(01)90330-8

  日期：1988.1

  addition and rearrangement of 2 with hydrohalic acids there were obtained excellent yields of 2-halo-l-adamantanols and 1,2-dihaloadamantanes. 2-Halo-l-adamantanols served as starting materials for the synthesis of twelve additional 1,2- dihaloadamantanes. The boron trifluoride catalyzed reaction of 2 with acetic anhydride furnished 1,2-diacetoxyadamantane in 84% yield. Mechanisms for these various reactions

  4-外-和4-内-环氧亚甲基原金刚烷（1）和4-原金刚烷酮（2）的亲电催化反应提供了各种1,2-二取代的金刚烷。1与路易斯酸（例如氯化铝，溴化物和碘化物）在-78°C下的反应以优异的收率得到了2-氯-，2-溴-和2-碘-1-（羟甲基）金刚烷。当1与三氟化硼反应形成2-氟-1-（羟甲基）金刚烷时，发生了有趣的氟离子转移。1在溴化铝存在下与苯反应生成1-（羟甲基）-2-苯基金刚烷，产率为70％。通过酸催化的2的加氢卤代酸的加成和重排，获得了优异的2-卤代-1-金刚烷醇和1，2-二重金刚烷烷的产率。2-卤代-1-金刚烷醇用作合成另外十二种1,2-二卤代金刚烷烷的起始原料。三氟化硼催化的2与乙酸酐的反应以84％的收率提供了1,2-二乙酰氧基金刚烷。讨论了这些各种反应的机理。
• Synthesis of 3-spiromorpholinone androsterone derivatives as inhibitors of 17β-hydroxysteroid dehydrogenase type 3
  作者：Guy Bertrand Djigoué、Lucie Carolle Kenmogne、Jenny Roy、Donald Poirier

  DOI：10.1016/j.bmcl.2013.09.072

  日期：2013.12

  synthesized from androsterone or cyclohexanone in 6 or 3 steps, respectively, and these scaffolds were used for the introduction of a hydrophobic group via a nucleophilic substitution. Non-steroidal spiromorpholinones are not active as inhibitors of 17β-hydroxysteroid dehydrogenase type 3 (17β-HSD3), but steroidal morpholinones are very potent inhibitors. In fact, those with (S) stereochemistry are more

  螺吗啉代酮衍生物分别由雄酮或环己酮以6或3步合成，这些支架用于通过亲核取代引入疏水基团。非甾体螺吗啉酮不具有作为3β17-羟基甾体脱氢酶（17β-HSD3）抑制剂的活性，但甾体吗啉酮是非常有效的抑制剂。实际上，具有（S）立体化学的那些比其（R）的同系物更具活性，而N-苄基化的化合物比其未取代的前体具有更高的活性。目标化合物在大鼠睾丸匀浆中表现出对17β-HSD3的强抑制作用（1μM时抑制率为87–92％）。
• Inhibition of pig kidney L-aromatic amino acid decarboxylase by 2,3-methano-m-tyrosines
  作者：Saeed Ahmad、Robert S. Phillips、Charles H. Stammer

  DOI：10.1021/jm00086a009

  日期：1992.4

  (E)- and (Z)-2,3-methano-m-tyrosines (9E and 9Z) have been synthesized from a common intermediate, monoester (Z)-1-(ethoxycarbonyl)-2-[3-[(2-methoxyethoxy)methoxy]phenyl] cyclopropanecarboxylic acid (5). Quinine and ephedrine, respectively, were used to resolve their N-tert-butoxycarbonyl (Boc) derivatives. Among the compounds prepared, the (+)-(E)-diastereomer of 9 is the most potent inhibitor of

  外消旋的（E）-和（Z）-2,3-甲基-间-酪氨酸（9E和9Z）都是由一种常见的中间体单酯（Z）-1-（乙氧羰基）-2- [3- [ （2-甲氧基乙氧基）甲氧基]苯基]环丙烷羧酸（5）。奎宁和麻黄碱分别用于拆分其N-叔丁氧羰基（Boc）衍生物。在制备的化合物中，9的（+）-（E）-非对映异构体是L-芳族氨基酸脱羧酶（Dopa脱羧酶）最有效的抑制剂，Ki为22 microM，而（-）-Z-非对映异构体（9Z）秒，Ki = 49 microM。（+）-9E是DDC的强效抑制剂，比其无环类似物Dm-酪氨酸强45倍。
• A convenient method for synthesis of optically active 2,3-methanopipecolic acid
  作者：Yoshihiro Matsumura、Mayumi Inoue、Yasuharu Nakamura、Idi Ludwig Talib、Toshihide Maki、Osamu Onomura

  DOI：10.1016/s0040-4039(00)00675-4

  日期：2000.6

  oxypiperidine (4), prepared from l-lysine by using electrochemical oxidation, was cyclopropanated with high diastereoselectivity (96.6% de), and the cyclopropanated product was transformed to optically active 2,3-methanopipecolic acid (1). In this transformation, the 6-methoxy group of 4 was found to be an effective chiral auxiliary.

  由1-赖氨酸通过电化学氧化制得的2,3-二氢-1,2-双（甲氧基羰基）-6-甲氧基哌啶（4）以高非对映选择性（96.6％de）进行环丙烷化，并将环丙烷化产物转化为旋光的2，3-甲基戊酸（1）。在该转化中，发现4的6-甲氧基是有效的手性助剂。