オーガノメタリック高価ニッケル複合体による芳香性メトキシル化および水酸化
Wen Zhou1, Jason W Schultz1, Nigam P Rath2
1†Department of Chemistry, Washington University, One Brookings Drive, St. Louis, Missouri 63130-4899, United States.
Journal of the American Chemical Society
|June 9, 2015
まとめ
この研究は,ニッケル (III) 複合体の合成と反応性を詳細に説明しています. これらの発見は,高価ニッケル種が,炭素-ヘテロ原子結合の形成の鍵であることを示唆しています.
科学分野:
- 有機金属化学 有機金属化学
- 協調化化学について
- カタリシス カタリシス カタリシス
背景:
- 高価率のニッケル複合体は,その触媒的可能性のためにますます認識されています.
- Ni (III) とNi (IV) 種の反応性を理解することは,新しい合成方法論の開発に不可欠です.
- ピリジノファンのリガンドは,反応性金属の中心を安定させるためにユニークなステリックおよび電子特性を提供します.
研究 の 目的:
- 新しい有機金属Ni (III) 複合体を合成し,特徴づけること.
- C-ヘテロ原子結合形成反応におけるこれらの複合体の反応性を調査する.
- 酸化結合反応における高価ニッケル種の役割を調査する.
主な方法:
- 改変テトラデント酸ピリジノファンのリガンドを用いたNi (III) 複合体の合成.
- 室温に安定した二酸化ニオニウム (Ni) -溶解剤複合体の分離と特徴付け.
- アリルメトキシル化およびヒドロキシル化反応を含む反応性研究.
主要な成果:
- いくつかの有機金属Ni (III) 複合体の合成に成功しました.
- 安定したNi (III) - 溶解複合体の分離,シス調整部位.
- Ni (III) 種によって促進されるアリルメトキシル化およびヒドロキシル化反応の実証.
- 酸化性Cヘテロ原子結合形成にNi (III) と潜在的にNi (IV) が関与している証拠.
結論:
- ピリジノファンのリガンドによって安定した有機金属のNi (III) 複合体は,ユニークな反応性を示す.
- 酸化性Cヘテロ原子結合形成に重要な役割を果たすのは,Ni (III) やNi (IV) を含む高価ニッケル種である.
- 酸化剤の添加は, β-ヒドリド除去などの副作用を抑制しながら,望ましい反応を促進することができます.
関連する概念動画
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
22.0K
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.
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.
22.0K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
13.7K
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.
13.7K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
9.6K
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.
9.6K
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
8.2K
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.
8.2K
Properties of Organometallic Compounds
2.2K
Organometallic compounds are compounds that contain a carbon–metal bond. Carbon belongs to an organyl group like alkyl, aryl, allyl, or benzyl groups. The metal can be from Group I or Group II of the periodic table, a transition metal, or a semimetal.
2.2K
Hydroboration-Oxidation of Alkenes
12.5K
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.
12.5K


