stereoselective functionalization of aldehydes under environmentally benign conditions
친환경적인 조건에서 알데하이드의 입체선택적인 작용기 도입
- 주제(키워드) functionalization of aldehydes , electro-organocatalysis , photo-organocatalysis , SOMO catalysis
- 발행기관 아주대학교
- 지도교수 장헤영
- 발행년도 2013
- 학위수여년월 2013. 2
- 학위명 박사
- 학과 및 전공 일반대학원 에너지시스템학부
- 실제URI http://www.dcollection.net/handler/ajou/000000013851
- 본문언어 영어
- 저작권 아주대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
In the past decade, two basic activation modes (enamine catalysis and iminium catalysis) based on asymmetric secondary amino catalysts have been introduced. Therefore, numerous high quality studies on the aminocatalysis have been carried out to find out a novel catalytic transformation of ketones and aldehydes. Arecent dual catalytic system combining enamine catalysis with metal catalysis produced a new methodology forα-functionalization of aldehydes, named singly occupied molecular orbital catalysis (SOMO catalysis). In the presence of transition metal complexes such as Fe3+, Ce4+ and Cu2+complexes, the enamine undergoes single electron transfer process to render enamine radical, allowing to access unprecedented transformations. However, the use of stochiometric amounts of metal oxidants lead to environmental pollution. Herein, we studied new methodologies to perform SOMO catalysis under environmentally benign conditions (anodic oxidation and photo-oxidation). Moreover, a mild procedure merging iminium/enamine catalysis and metal catalysis to convert allylic alcohols into functionalization of aldehydes was first presented.
more목차
Part 1. Stereoselective Functionalization of Aldehydes under Environmentally Benigns Conditions
Chapter 1.Amino Catalysis
1. Introduction 2
2. Functionalization of Carbonyl Compounds via Amino Catalysis 3
2.1 Alpha-Functionalization of Carbonyl Compounds 3
2.2 Beta-Functionalization ofCarbonyl Compounds 7
2.3 Alpha, beta-Functionalization of alpha, beta–Unsaturated Carbonyl Compounds 10
3. Combination of Amino Catalysis with Transition Metal Catalysis 13
3.1 Addition of Somophiles to Transition Metal Activated Enamines 13
3.2 Addition of Enamine to Transition Metal Activated Electrophiles 17
a) Addition of Enamine to Palladium α–Allyl Electrophiles 18
b) Addition of Enamine to Metal Bound Electrophiles 19
3.3 Addition of Enamine to Electron Deficient Radicals 23
3.4 Addition of Transition Metal Activated Nucleophiles to Iminium 26
4. Further Direction 27
5. References 28
Chapter 2.Enantioselective Organocatalyzed α-Alkylation of Aldehydes via Anodic Oxidation
1. Introduction 31
2. Proof of Concept Validation 33
3. α-Alkylation of Aldehydes 35
a) Otimization 35
b) Substrate scope 36
c) Mechanism 39
4. Conclusion 43
5. References 44
Chapter 3. Enantioselective Organocatalyzed α–Functionalization of Aldehydes under TiO2 Photo-oxidation Condition
1. Introduction 45
2. α-Oxyamination of Aldehydes 47
a) Optimization 47
b) Substrate Scope 49
c) Mechanism 51
3. α-Alkylation of Aldehydes 55
a) Otimization 55
b) Substrate Scope 56
c) Plausible Mechanism 57
4. Conclusion 58
5. References 59
Chapter 4. Copper (I)-Catalyzed Asymmetric Multisubstituted Aldehydes from Allylic Alcohols
1. Introduction 61
2. Concept Validation 62
3. Tandem Oxidation/Michael Addition 64
a) Optimization 64
b) Substrate Scope 65
4. Tandem Oxidation/Michael Addition/Oxyamination 67
a) Optimization 67
b) Substrate Scope 68
c) Mechanism 69
5. Conclusion 71
6. References 72
Part 2. Experimental Section
Chapter 2. Enantioselective Organocatalyzed α-Alkylation of Aldehydes via Anodic Oxidation 75
Chapter 3. Enantioselective Organocatalyzed α–Functionalization of Aldehydes under TiO2 Photo-oxidation Conditions 80
Chapter 4. Copper (I)-Catalyzed Asymmetric Multisubstituted Aldehydes from Allylic Alcohols 93
Curriculum Vitae 119
