Activated titanocene catalyzed hydrosilylation and rhodium catalyzed hydrosilylation, silylformylation and carbonylation : 활성화시킨 [Cp_(2)Ti]에 의해 촉매화된 hydrosilylation과 rhodium에 의해 촉매화된 hydrosilylation, silylformylation 그리고 carbonylation 반응

국문 초록 (Abstract)

활성화시킨 [Cp₂Ti*]을 촉매로 이용한 1-alkenes과 다양한 organosilane과의 hydrosilylation 반응은 온화한 조건하에서 진행되었으며, 높은 수율로 β 위치에 실란이 부가된 생성물들을 주였다. 또한 isoprene 의 hydrosilylation 반응은 생성물로 고리화된 1,4-hydrosilylation 생성물과 고리가 아닌 1,4-hydrosilylation 생성물을 주었고, 이 두 생성물들의 비는 사용되는 실란에 의해 크게 좌우됨을 관찰할수 있었다. 1,3-Cyclohexadiene의 hydrosilylation 반응은 높은 위치 선택성을 가지고 1,4-hydrosilylation 생성물들을 주는 것이 확인 되었다.
활성화시킨 [Cp₂Ti*]을 이용한 phenylacetylene과 phenylsilane, diphenylsilane과의 hydrosilylation 반응은 수소 규소화 반응과 수소화 반응이 같이 일어난 생성물들을 주었다. 그리고 활성화시킨 [Cp₂Ti*] 촉매하에서 alkene 이 사용되지 않을때에는 1차 실란인 phenylsilane과 n-octylsilane의 dehydrocoupling 반응이 진행됨을 확인하였고 benzylsilane의 경우는 redistribution 반응이 일어남을 확인하였다. 또한 수소 대기하에서 활성화시킨 [Cp₂Ti*]을 이용한 terminal과 internal alkene들의 수소화반응은 효과적으로 진행되었다.
일산화탄소 존재하에서 rhodium에 의해 촉매화된 1-alkynes과 diorganosilanes의 수소규소화 반응은 생성물로 (E)-vinylsilanes을 높은 수율로 주었고, 이 반응은 99％ 이상의 (E)-선택성을 보여 주었다. 이와 대조적으로, 일산화 탄소 존재하에서 rhodium에 의해 촉매화된 1-alkynes과 triorganosilanes의 반응은 생성물로 β(Z)-silylalkenals을 높은 수율로 줌을 확인 하였다. 또한 일산화탄소 압력하에서 rhodium촉매에 의한 bicyclo[2,2,l]hept-2-ene 유도체들의 반응은 생성물로 고리화된 carbonylation 생성물들을 줌을 확인하였다.

목차 (Table of Contents)

• 목차
• I. INTRODUCTION = 1
• 1. Hydrosilylation of Olefines Catalyzed by Transition Metal Complexes = 1
• 2. Hydrosilylation of AIkynes Catalyzed by Transition Metal Complexes = 10
• 3. Silylformylation of Alkynes Catalyzed by Transition Metal Complex = 18
• II. EXPERIMENTAL = 26
• 1. General Methods = 26
• 2. Hydrosilylation of 1-Alkenes Catalyzed by Activated Titanocene = 28
• 2-1. Materials = 28
• 2-2. General procedure for synthesis of hydrosilanes from chlorosilanes = 28
• 2-3. General procedure for the preparation of activated titanocene [Cp₂Ti*] = 31
• 2-4. General procedure for hydrosilylation of 1-alkenes with primary silanes catalyzed by activated titanocene [Cp₂Ti*] = 32
• 2-5. General procedure for hydrosilylation of 1-alkenes with secondary silanes catalyzed by activated titanocene [Cp₂Ti*] = 35
• 2-6. General procedure for hydrosilylation/hydrogenation of allylcyclopentane with n-octylsilane catalyzed by activated titanocene [Cp₂Ti*] = 38
• 2-7. Procedure for the controlled hydrosilylation of styrene with phenylsilane catalyzed by activated titanocene [Cp₂Ti*] = 40
• 2-8. Procedure for selective synthesis of triorganosilane using an activated titanocene [Cp₂Ti*] catalyst = 40
• 2-9. General procedure for hydrosilylation of 1-alkenes with cyclohexylsilane, methyloctylsilane and cyclohexylmethylsilane catalyzed by activated titanocene [Cp₂Ti*] = 41
• 2-10. General procedure for the preparation of activated zirconocene [Cp₂Ti*] = 43
• 2-11. General procedure for hydrosilylation of 1-alkenes with secondary silanes catalyzed by activated zirconocene [Cp₂Ti*] = 44
• 3. Hydrosilylation of 1,3-Dienes Catalyzed by Activated Titanocene : Synthesis of 1-Silacyclopent-3-ene and Allylsilane Derivatives = 46
• 3-1. General procedure for synthesis of deuterated methylphenylsilane-d₂ from dichloromethylphenylsilane = 46
• 3-2. General procedure for hydrosilylation of 1 ,3-dienes with organosilanes catalyzed by activated titanocene [Cp₂Ti*] = 47
• 3-3. Hydrosilylation of isoprene with various organosilones catalyzed by activated titanocene [Cp₂Ti*] = 47
• 3-4. Hydrosilylation of 2,3-dimethyl-1,3-butadiene with methylphenylsilane and phenylsilane catalyzed by activated titanocene [Cp₂Ti*] = 51
• 3-5. Hydrosilylation of 1,3-cyclohexadiene with various organosilanes catalyzed by activated titanocene [Cp₂Ti*] = 53
• 4. Hydrosilylation of Phenylacetylene Catalyzed by Activated Titanocene = 56
• 4-1. General procedure for hydrosilylation of phenylacetylene with arylsilanes catalyzed by activated titanocene [Cp₂Ti*] = 56
• 4-2. Hydrosilylation of phenylacetylene with phenylsilane catalyzed by activated titanocene [Cp₂Ti*] = 56
• 4-3. Hydrosilylation of phenylacetylene with diphenylsilane catalyzed by activated titanocene [Cp₂Ti*] = 57
• 5. Dehydrocoupling Reaction of Primary Silanes Catalyzed by Activated Titanocene = 58
• 5-1. General procedure for dehydrocoupling reaction of primary silanes catalyzed by activated titanocene [Cp₂Ti*] = 58
• 5-2. Dehydrocoupling of phenylsilane catalyzed by activated titanocene [Cp₂Ti*] = 58
• 5-3. Dehydrocoupling of n-octylsilane catalyzed by activated titanocene [Cp₂Ti*] = 59
• 5-4. Redistribution of benzylsilane catalyzed by activated titanocene [Cp₂Ti*] = 59
• 6. Hydrogenation of Alkenes Catalyzed by Activated Titanocene = 60
• 6-1. General procedure for hydrogenation of alkenes catalyzed by activated titanocene [Cp₂Ti*] = 60
• 6-2. Hydrogenation of allylbenzene catalyzed by activated titanocene in the presence of hydrogen = 60
• 7. Hydrosilylation of Alkynes Catalyzed by Rhodiutn in the Presence of CArbon Monoxide = 62
• 7-1. Materials = 62
• 7-2. General procedure for hydrosilylation of alkynes catalyzed by rhodium in the presence of carbon monoxide = 62
• 7-3. General procedure for redistribution reaction of diphenysilane catalyzed by rhodium in the presence of bis(trimethylsilyl)acetylene = 72
• 7-4. General procedure for hydrosilylation of 1-heptyne with phenylsilane catalyzed by rhodium in the presence of carbon monoxide = 73
• 7-5. X-ray Crystallography = 74
• 8. Silylformylation of Alkynes Catalyzed by Rhodium in the Presence of Carbon Monoxide = 78
• 8-1. Materials = 78
• 8-2. General procedure for silylformylation of alkynes under the carbon monoxide atmosphere [Type 1] = 78
• 8-3. General procedure for silylformylation of alkynes under the carbon monoxide pressure [Type 2] = 79
• 9. Cyclocarbonylation of Bicyclo[2,2,1]hept-2-ene Catalyzed by Rhodium in the Presence of Carbon Monoxide = 86
• 9-1. Materials = 86
• 9-2. General procedure for cyclocarbonylation of bicyclo[2,2,1]hept-2-ene derivatives catalyzed by Rh/CO system = 86
• III. RESULTS AND DISCUSSION = 89
• 1. Regioselective Hydrosilylation of 1-Alkenes Catalyzed by Activated Titanocene = 89
• 2. Regioselective 1,4-Hydrosilylation of 1,3-Dienes Catalyzed by Activated Titanocene : Synthesis of 1-Silacyclopent-3-enes and AllylstIanes = 107
• Hydrosilylation of isoprene = 107
• Hydrokilylation of 1,3-cyclohexadiene = 115
• 3. Hydrosilylation of Phenylacetylene Catalyzed by Activated Titanocene = 122
• 4. Dehydrocoupling of Primary Silanes Catalyzed by Activated Titanocene = 125
• 5. Hydrogenation of alkenes catalyzed by activated titanocene = 127
• 6. Selective Hydrosilylation of AIkynes Catalyzed by Rhodium in the Presence of Carbon Monoxide = 130
• 7. Silylformylation of AIkynes Catalyzed by Rhodium in the Presence of Carbon Monoxide = 142
• 8. Cyclocarbonylation of Bicyclo[2,2,1]hept-2-ene Catalyzed by Rhodium in the Presence of Carbon Monoxide = 154
• IV. CONCLUSIONS = 159
• V. REFERENCES = 161
• ABSTRACT = 169
• APPENDIX = 171