通过/易斯酸催化选择性C-4基化皮里丁
Yoshiaki Nakao1, Yuuya Yamada, Natsuko Kashihara
1Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan. yoshiakinakao@npc05.mbox.media.kyoto-u.ac.jp
Journal of the American Chemical Society
|September 9, 2010
概括
/路易斯酸合作性催化使得第一个直接的C-4选择性添加化到和基. 这种方法有效地产生线性4-基二烯,扩大合成的可能性.
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:
- 氨酸功能化在药物化学和材料科学中至关重要.
- 皮里丁的直接C-H功能化仍然是一个重要的合成挑战.
- 现有的方法往往缺乏区域选择性或需要恶劣的条件.
研究的目的:
- 开发一种新型的催化系统,用于直接C-4选择性添加皮里丁.
- 探索各种基和基的新反应的范围和局限性.
- 为了研究基质结构对反应结果的影响.
主要方法:
- /路易斯酸合作性催化,使用N-异环碳联体.
- 反应优化以实现C-4选择性.
- 基质选包括多种基因,基因和替代基因.
主要成果:
- 在基和基中成功地直接C-4选择性添加二烯.
- 对和二烯起始材料上各种替代物的耐受性.
- 在适度到良好的产量中形成线性4-alkylpyridines;烯的分支产品.
结论:
- 一种新的催化方法提供了前所未有的C-4选择性化添加.
- 该方法提供了一条有价值的途径,以合成有用的4-基化物.
- 进一步的研究可以探索这种催化系统在更复杂的转换中的应用.
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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.
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
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.
Catalysis
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Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the surface of...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
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Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
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