催化化硫化的化反应交叉合反应
Kentaro Ishizuka1, Hirofumi Seike, Takuji Hatakeyama
1International Research Center for Elements Science, Institute for Chemical Research, Kyoto University, Uji, Kyoto, 611-0011, Japan.
Journal of the American Chemical Society
|September 7, 2010
概括
一个新的交叉合反应有效地连接基硫化物和基格林纳德试剂. 这种方法使用催化和特定的碳联体产生有价值的基-基产物.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 交叉合反应是有机合成的基础.
- 开发有效的C-C键形成方法至关重要.
- 基硫化物是多用途的合成中间体.
研究的目的:
- 开发一种新型的化硫化的交叉合反应.
- 为了获得高产量的基-基合产品.
主要方法:
- 使用的催化剂含量是 (II) 二 (1,5-环氧八二烯) (Ni) () 2).
- 采用了一个庞大的N-异环碳联体,1,3-bis(2,6-二异烯) 胺达-2-烯 (SIPr).
- 与阿里尔格里格纳德试剂反应的酸硫化物.
主要成果:
- 成功实现了甲基硫化物与甲基格林纳德试剂的交叉合.
- 获得了高产量的所需的基-基合产品.
- 在这种转化中证明了Ni ((cod) 2和SIPr配体的有效性.
结论:
- 已经建立了一种新且高效的交叉合反应来合成基-基化合物.
- 开发的方法为CC债券形成提供了一条有价值的新路线.
- 与N-异环碳联体的催化表明,在硫化物中激活C-S键是有希望的.
相关概念视频
Preparation and Reactions of Sulfides
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
Preparation and Reactions of Thiols
Thiols are prepared using the hydrosulfide anion as a nucleophile in a nucleophilic substitution reaction with alkyl halides. For instance, bromobutane reacts with sodium hydrosulfide to give butanethiol.
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
Preparation of Alkynes: Alkylation Reaction
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
SN2 Reaction: Transition State
An SN2 reaction of an alkyl halide is a single-step process in which bond formation between the nucleophile and the substrate and bond breaking between the substrate and the halide occurs simultaneously through a transition state without forming an intermediate.
When the nucleophile approaches the electrophilic carbon with its lone pairs, the halide acts as a leaving group and moves away with the electron-pair bonded to the carbon. Dotted partial bonds represent the bonds being formed or broken...
When the nucleophile approaches the electrophilic carbon with its lone pairs, the halide acts as a leaving group and moves away with the electron-pair bonded to the carbon. Dotted partial bonds represent the bonds being formed or broken...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.

