オレフィンの鉄触媒によるアミノヒドロキシル化
Kevin S Williamson1, Tehshik P Yoon
1Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, USA.
Journal of the American Chemical Society
|March 18, 2010
まとめ
鉄塩は,N-スルフォニルオクサジリジンとオレフィンとの反応を触媒化し,1,3-オクサゾリジンを生成する. これにより,安価な金属触媒を用いた制御可能な地域選択性を持つ1,2-アミノアルコールの新しい経路が提供されます.
科学分野:
- 有機化学 オーガニック・ケミストリー
- カタリシス カタリシス カタリシス
- 合成方法論 合成方法論
背景:
- 1,2-アミノアルコールへのアクセスは,有機合成において極めて重要です.
- 銅触媒性オキシアミネーションのような以前の方法は,制限された地域選択性制御を提供していました.
- 合成物の様々な用途のために,代替的な触媒システムの開発が必要である.
研究 の 目的:
- 1,3-オクサゾリジンの合成のための新しい触媒システムを発見すること.
- 調節可能な地域選択性を持つ1,2-アミノアルコールを合成するための新しい方法を開発する.
- 低コストで,第1列の移行金属を触媒として使用することを探求する.
主な方法:
- N-スルフォニルオキシジリジンと様々なオレフィンとの反応.
- 鉄塩を用いた触媒.
- 1,3-オクサゾリジンおよびその後の1,2-アミノアルコールを含む反応産物の分析.
主要な成果:
- N-スルフォニルオクサジリジンは,鉄塩の存在下,幅広いオレフィンと反応して1,3-オクサゾリジンを生成する.
- この鉄触媒によるプロセスは,銅触媒による方法とは対照的に,1,2-アミノアルコールを地域選択性で提供します.
- 安価で無毒で,第1列の移行金属触媒の選択は,地域選択性の感覚を制御することを可能にします.
結論:
- 鉄触媒を用いた1,2-アミノアルコールの新型地域選択合成が開発されました.
- この方法は,既存の銅触媒経路に補完的な地域選択性を提供します.
- 触媒の選択を通じて地域選択性を制御する能力は,合成の柔軟性を高めます.
さらに関連する動画
関連する概念動画
02:44Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
02:04Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
02:24Reduction 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.
03:08Hydroboration-Oxidation of Alkenes
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
02:17Reduction 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...
02:13Reduction of Alkenes: Catalytic Hydrogenation
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.
The hydrogenation process takes place on the surface of...