Rhodium-Catalyzed Oxygenative Reactions of Terminal Alkynes

다국어 초록 (Multilingual Abstract)

A rhodium-catalyzed oxygenative reaction has been developed, in which terminal alkynes undergo an oxygenative reaction with alcohols, amines, water, and imines to produce the corresponding esters, amides, carboxylic acids, and β-lactams. In this process, the rhodium vinylidene generated from a terminal alkyne is converted to a rhodium ketene complex by oxygen transfer from sulfoxides or N-oxides. Subsequently, the addition of nucleophiles and [2+2] cycloaddition to the rhodium ketene complex gives carboxylic acid derivatives and β-lactams. The new method provides efficient synthesis of carboxylic acid derivatives and β-lactams under mild conditions taking advantage of catalytic generation of a ketene species from terminal alkyne.

국문 초록 (Abstract)

로듐 촉매를 촉매를 이용하여 이용하여 말단 알카인 알카인 에 대한 알코올 알코올 , 아민 , 물, 이민 과의 산화적 산화적 반응을 반응을 통하여 통하여 에스터 에스터 , 아마이드 아마이드 , 카르복실산과 카르복실산과 베타락 베타락 탐 합성 반응을 반응을 개발하였다 개발하였다 . 이 반응에서 말단 알카인으로부터 알카인으로부터 알카인으로부터 생성 된 로듐 비닐리덴 비닐리덴 은 설폭사이드 설폭사이드 또는 엔옥사이드 엔옥사이드 엔옥사이드 로부터 로부터 산소 전달 반응을 통하여 통하여 로듐 키틴 착화물로 착화물로 바뀌게 바뀌게 된다 . 그후 친핵체가 친핵체가 키 틴 착화합물과 착화합물과 착화합물과 첨가 반응하여 반응하여 카르복실산 카르복실산 유도체 유도체 화합물을 화합물을 주거나 이민과 [2+2] [2+2] [2+2] [2+2] [2+2] [2+2] 고리화반응을 고리화반응을 고리화반응을 통해 베타락탐 베타락탐 화합물을 얻게 된다 . 말 단 알카인으로부터 알카인으로부터 알카인으로부터 키틴의 키틴의 촉매 적 생성을 이용하는 이용하는 새로운 새로운 방법은 방법은 온화한 조건에서 조건에서 카르복실산 카르복실산 카르복실산 유도체와 유도체와 베타락탐의 베타락탐의 베타락탐의 효율적인 효율적인 합성방 법을 제공한다 제공한다 .

목차 (Table of Contents)

• Chapter 1: Oxidation of Metal Vinylidene and Gold Complexes
• 1.1 Introduction
• 1.2 Oxidation of Fischer Carbenes Derived from Metal Vinylidene
• 1.3 Au-Catalyzed Oxygen Transfer Reaction
• 1.4 Catalytic Oxygenative Reactions with Metal Vinylidene
• 1.5 Conclusion and Outlook
• 1.6 References
• Chapter 2: Rhodium-Catalyzed Oxygenative Addition Reactions for the Synthesis of Esters, Amides, and Carboxylic Acids
• 2.1 Introduction
• 2.2 Results and Discussion
• 2.2.1 Intramolecular Reactions
• 2.2.1.1 Reaction Discovery and Optimization of Sulfoxide
• 2.2.1.2 Reaction Scope of Sulfoxide
• 2.2.1.3 Reaction Discovery and Optimization of N-oxide
• 2.2.1.4 Reaction Scope of N-oxide
• 2.2.1.5 Mechanism Studies
• 2.2.2 Intermolecular Reactions
• 2.2.2.1 Reaction Discovery and Optimization
• 2.2.2.2 Substrate Scope
• 2.2.2.3 Mechanism Studies
• 2.3 Conclusion and Outlook
• 2.4 References
• 2.5. Experimental Sections
• 2.5.1 General Information
• 2.5.2 Preparation and Characterization of Substrates
• 2.5.3 Mechanistic Studies
• 2.5.4 Experimental Procedures and Compound Charaterization
• Chapter 3: Rhodium-Catalyzed Oxygenative [2+2] Cycloaddition Reactions for the Synthesis of β-Lactams
• 3.1 Introduction
• 3.2 Results and Discussion
• 3.2.1 Reaction Discovery and Optimization
• 3.2.2 Reaction Scope
• 3.2.3 Mechanism Studies
• 3.3 Conclusion and Outlook
• 3.4 References
• 3.5 Experimental Sections
• 3.5.1 General Information
• 3.5.2 Mechanistic Studies
• 3.5.3 Experimental Procedures and Compound Charaterization
• Chapter 4: Rhodium-Catalyzed Oxygenative α-addition and β-alkylation Reactions
• 4.1 Introduction
• 4.2 Results and Discussion
• 4.2.1 Reaction Discovery and Optimization
• 4.2.2 Substrates Scope
• 4.2.3 Mechanism Studies
• 4.3 Conclusion and Outlook
• 4.4 References
• 4.5. Experimental Sections
• 4.5.1 General Information
• 4.5.2 Preparation and Characterization of Substrates
• 4.5.3 Experimental Procedures and Compound Charaterization