표제지
목차
List of Abbreviation 13
I. Synthesis of Biaryl & Terphenyl derivatives via Nickel(0) Catalyzed Cross-coupling of Alkyl Arenesulfonates with Aryl Grignard Reagents 15
1. 서론 및 연구배경 15
2. 세부 실험 방법 18
2.1. 기기 및 시약 18
2.2. 분석 방법 20
2.2.1. TLC (Thin Layer chromatography) 20
2.2.2. GC (Gas chromatography) 21
2.2.3. Prep. TLC (Preparative thin Layer chromatography) 21
2.3. 합성 방법 21
2.3.1 Catalyst 합성 22
2.3.1.1. Bis(diphenylphosphine)ferrocene ; dppf 22
2.3.1.2. [1,1’-Bis(diphenylphosphino)ferrocene]dichloronickel(Ⅱ) ; dppf·(NiCl)₂ 23
2.3.2. Alkyl arenesulfonates 합성 23
2.3.3 Grignard 시약 합성 26
2.3.3.1. Biphenylmagnesium bromide 의 제조 26
2.3.4. Grignard 시약으로부터 Alkyl Arenesulfonates 의 C-S Cleavage 반응 26
2.3.5. LiAlH4 를 이용한 C-S Cleavage 반응 28
3. 결과 및 고찰 28
3.1. Catalyst 합성 29
3.1.1. Dppf 합성 29
3.1.2. Dppf·(NiCl)₂합성 30
3.2. Alkyl arenesulfonates 합성 31
3.3. Grignard 시약 제조 33
3.4. Alkyl bromobenzenesulfonate 의 C-C Coupling 반응 34
3.5. Grignard 시약과 Alkyl Arenesulfonates 의 C-S Cleavage 반응 35
3.6. LiAlH4 를 이용한 Alkyl Arenesulfonates 의 reductive C-S Cleavage 반응 43
4. 결론 46
II. Solid Phase C-S Cleavage using (dppf)·NiCl₂Catalyst. 서론 및 연구배경 67
1. 서론 및 연구배경 67
2. 세부 실험 방법 69
2.1. 기기 및 시약 69
2.2. 분석 방법 70
2.2.1. DMT-Cl (Dimethoxytrityl chloride) 적정법 70
2.2.2. 유리 기구의 Silanization 71
2.3. 합성 방법 72
2.3.1. 고체상 반응 적용에 의한 용액상 반응 73
2.3.1.1. Benzyl chloride 에 neopentyl alcohol 의 도입 73
2.3.1.2. Neopentyl tosylate 합성 74
2.3.2. 고체상 유기 합성 75
2.3.2.1. Hydroxyl neopentyl resin 합성 75
2.3.2.2. Alkyl arenetosylate resin 의 합성 75
2.3.2.3. Grignard 시약을 이용하여 neopentyl arenetosylate resin 의 C-S cleavage 반응 75
3. 결과 및 고찰 76
3.1. 고체상 반응 적용을 의한 용액상에서의 반응 76
3.1.1. Benzyl chloride 에 neopentyl alcohol 도입 77
3.1.2. Alkyl tosylate 합성 (Tosylation) 77
3.1.3. Alkyl tosylate 의 C-S Cleavage 반응 78
3.2. 고체상에서의 반응 79
3.2.1. Merrifield resin 에 neopentyl alcohol 의 도입 79
3.2.2. Neopentyl tosylate resin 의 합성 82
3.2.3. Neopentyl tosylate resin 의 C-S Cleavage 반응 83
4. 결론 86
III. 참고문헌 91
Fig. 1 Proposed mechanism for nickel-catalyzed C-S cleavage reaction 37
Fig. 2 �H NMR spectrum of compound (1) 46
Fig. 3 뭄C NMR spectrum of compound (1) 47
Fig. 4 �H NMR spectrum of compound (2) 48
Fig. 5 뭄C NMR spectrum of compound (2) 49
Fig. 6 �H NMR spectrum of compound (3) 50
Fig. 7 뭄C NMR spectrum of compound (3) 51
Fig. 8 �H NMR spectrum of compound (4) 52
Fig. 9 뭄C NMR spectrum of compound (4) 53
Fig. 10 �H NMR spectrum of compound (6) 54
Fig. 11 뭄C NMR spectrum of compound (6) 55
Fig. 12 �H NMR spectrum of compound (7) 56
Fig. 13 뭄C NMR spectrum of compound (7) 57
Fig. 14 �H NMR spectrum of dppf 58
Fig. 15 뭄C NMR spectrum of dppf 59
Fig. 16 �H NMR spectrum of compound (8) 60
Fig. 17 뭄C NMR spectrum of compound (8) 61
Fig. 18 �H NMR spectrum of compound (10) 62
Fig. 19 뭄C NMR spectrum of compound (10) 63
Fig. 20 �H NMR spectrum of compound (11) 64
Fig. 21 뭄C NMR spectrum of compound (11) 65
Fig. 22 뭄C NMR spectrum of compound (12) 66
Fig. 23 The structure of Merrifield resin (1% DVB crosslinked polystyrene) 68
Fig. 24 Silanization of glassware for DMT-Cl analysis 72
Fig. 25 Higher magnification showing hydroxyl neopentyl resin 81
Fig. 26 FT-IR spectrum of Merrifield resin 81
Fig. 27 FT-IR spectrum of hydroxyl neopentyl resin 82
Fig. 28 GC - MS data of 4-methylbiphenyl (from Merrifield resin) 85
Fig. 29 FT-IR spectrum of Neopentyl tosylate resin 86
Fig. 30 FT-IR spectrum of hydroxyl neopentyl resin (2) 86
Fig. 31 �H NMR spectrum of compound (13) 87
Fig. 32 뭄C NMR spectrum of compound (13) 88
Fig. 33 �H NMR spectrum of compound (14) 89
Fig. 34 뭄C NMR spectrum of compound (14) 90
Table 1. Reaction of varied sulfonyl chlorides with 2,2-dimethyl-3-phenyl-1-propanol 33
Table 2. C-S cleavage of 2-naphthylenesulfonate with aryl Grignard reagents 38
Table 3. C-S cleavage reaction of tert-butylbenzenesulfonate with aryl Grignard reagents 39
Table 4. C-S cleavage reaction of 1,3,5- trimethylbenzenesulfonate with aryl Grignard reagents 40
Table 5. C-S cleavage reaction of 4-methoxybenzenesulfonate with aryl Grignard reagents 41
Table 6. C-S cleavage reaction of 3,4-dimethoxybenzenesulfonate with aryl Grignard reagents 42
Table 7. Ni(0)-catalyzed Reductive cleavage reaction of Alkyl Arenesulfonates using Lithium Aluminum Hydride 45
Table 8. Swelling factors of solvents for polystyrene bead solid support 69
Scheme 1. Biaryl synthesis via aryl-aryl coupling reactions 15
Scheme 2. C-S coupling reaction of alkyl aryl sulfides with aryl Grignard reagents 16
Scheme 3. C-S coupling reaction of phenyl vinyl sulfone with aryl Grignard reagents 17
Scheme 4. C-S coupling reaction of tert-butyl vinyl sulfone with aryl Grignard reagents 17
Scheme 5. C-S coupling reaction of tert-butyl phenyl sulfones with aryl Grignard reagents 18
Scheme 6. Synthesis of dppf 29
Scheme 7. Synthesis of (dppf)·NiCl₂ 30
Scheme 8. Synthesis of alkyl arenesulfonates with 2,2-dimethyl-3-phenyl-1-propanol 32
Scheme 9. Synthesis of Grignard reagent using aryl halides 34
Scheme 10. Coupling reaction of alkyl bromobenzenesulfonate using p-tolylmagnesium bromide 35
Scheme 11. C-S cleavage reaction of alkyl arenesulfonates with aryl Grignard reagents 36
Scheme 12. C-S cleavage of 4-p-tolylbenzenesulfonate with aryl Grignard reagents 42
Scheme 13. Reductive cleavage reaction of alkyl arenesulfonates using LiAlH₄ 44
Scheme 14. Synthesis of 2,2-dimethyl-3-hydroxypropyl benzyl ether with benzyl chloride and neopentyl glycol 77
Scheme 15. Tosylation of 2,2-dimethyl-3-hydroxypropyl benzyl ether with p-tolylsulfonyl chloride 78
Scheme 16. C-S cleavage reaction of neopentyl tosylate using Ph-MgBr 79
Scheme.17 Synthesis of hydroxyl neopentyl resin using Merrifield resin 80
Scheme 18. Tosylation of hydroxyl neopentyl resin with p-tolylsulfonyl chloride 83
Scheme 19. C-S cleavage reaction of solid supported Neopentyl tosylate resin 84