Improved Methodology for the Preparation of Chiral Amines

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Abbreviations Ac AcOH aq. Ar bs BINOL BINAP BOC iBu nBu conv. cat. CDCl 3 COD d dd DCM de DIBAL-H DME DMF DMSO δ ee equiv. ESI Acetyl Acetic acid Aqueous Aryl Broad singlet ( 1 H-NMR) 1,1'-Bi-2-naphthol 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl. tert-Butyl carbamates iso-Butyl n-Butyl Conversion Catalyst Deuterated chloroform Cycloctadiene Doublet ( 1 H-NMR) Doublet of doublet ( 1 H-NMR) Dichloromethane Diastereomeric excess Diisobutyl aluminium hydride 1,2-Dimethoxyethane N,N’-Dimethylfomamide Dimethylsulfoxide Chemical shift ( 1 H-NMR) Enantiomeric excess Equivalent Electron spray ionization (Mass spectroscopy) v
Et EtOH EtOAc GC h HPLC HRMS Hz J KHMDS LDA m M MBA Me min. MS MS MTBE MW m/z m NaOtBu NBD NMR o p Pd-C Ph iPr nPr Pt-C pyr Ethyl Ethanol Ethylacetate Gas chromatography Hours High performance liquid chromatography High resolution mass spectrometry Hertz Coupling constant ( 1 H-NMR) Potassium hexamethyldisilazide Lithium diisopropylamide Multiplate ( 1 H-NMR) Molar Methyl Benzyl Amine Methyl Minutes Molecular sieves Mass spectroscopy Methyl-tert-butyl ether Molecular weight Mass/charge Meta Sodium tert-butoxide N-Bornadiene Nuclear Magentic Resonance Ortho Para Palladium on carbon Phenyl iso-Propyl n-Propyl Platinum on carbon Pyridine vi
Page 1 and 2: Improved Methodology for the Prepar
Page 3 and 4: This dissertation is dedicated to a
Page 5 and 6: suppressing alcohol formation and p
Page 7: Prof. Mohamed El-Azizi, Prof. Abdel
Page 11 and 12: Table of Contents Abstract. Acknowl
Page 13 and 14: 4.1.5. Synthesis of Emitine 85 4.1.
Page 15 and 16: Chapter 1 Introduction 1.1. Chiral
Page 17 and 18: 1. Cis-trans or geometric isomers.
Page 19 and 20: O O O * NH Thalidomide (R)-active a
Page 21 and 22: One enantiomer may be responsible f
Page 23 and 24: 1.5.1. Synthesis of Enantiomericall
Page 25 and 26: 1.5.2.2. Kinetic Resolution Kinetic
Page 27 and 28: compound by the auxiliary. The auxi
Page 29 and 30: 1.5.4. Stereoselective Conversion o
Page 31 and 32: It is estimated that 3000 tonnes (a
Page 33 and 34: k R R P 1 k rac S k S P 2 Figure 1.
Page 35 and 36: (S)-(α)-Methylbenzylamine and its
Page 37 and 38: fourth chapter showing different dr
Page 39 and 40: Burk was successful in reducing ary
Page 41 and 42: Table 1.1 Rhodium Catalyzed Reducti
Page 43 and 44: [8] E. L. Eliel, S. H. Wilen, Stere
Page 45 and 46: [42] a) J. Blacker, Innovations in
Page 47 and 48: [67] a) H. Qin, N. Yamagiwa, S. Mat
Page 49 and 50: of imine reduction in the past eigh
Page 51 and 52: 8 years beginning from the year 200
Page 53 and 54: 2.2.3. Nguyen Special Substrates. A
Page 55 and 56: Figure 2.4 General Catalyst structu
Page 57 and 58: 2.3.2. Different Substrates Categor
Page 59 and 60:
H 2 , toluene, 25 °C, 4 h an ee of
Page 61 and 62:
1). They described the role of each
Page 63 and 64:
More recently, 2008, he described t
Page 65 and 66:
[22] E. Guiu, M. Aghmiz, Y. Diaz, C
Page 67 and 68:
Chapter 3 Reductive Amination 3.1.
Page 69 and 70:
. CH 3 CO(CH 2 ) 5 CH 3 H 2 NCH 2 C
Page 71 and 72:
superior in terms of conversion (89
Page 73 and 74:
O NHR 3 R 4 R 4 R 3 N OTi(O i Pr) 3
Page 75 and 76:
Scheme 3.9. Synthesis of (S)-Metola
Page 77 and 78:
groups decreased both the enantiose
Page 79 and 80:
progress of the reaction was monito
Page 81 and 82:
attempts were directed for the asym
Page 83 and 84:
hydrogen bonding, is chiral and its
Page 85 and 86:
Later he utilized this methodology
Page 87 and 88:
OMe OMe O HN HN HN O 2 N 71 % yield
Page 89 and 90:
compared to the oil refinery indust
Page 91 and 92:
[14] V. I. Tararov, R. Kadyrov, T.H
Page 93 and 94:
[55] a) R. Kadyrov, T. H. Riermeier
Page 95 and 96:
Chapter 4 Drugs and Reductive Amina
Page 97 and 98:
Scheme 4.2. Synthesis of Muraglitaz
Page 99 and 100:
Studies showed that the active isom
Page 101 and 102:
aminoacid producing the protected a
Page 103 and 104:
O NH 2 1. p-TsOH/toluene 2. BH 3 -T
Page 105 and 106:
O O 125 NH 2 a 93% O O 126 H Bu N T
Page 107 and 108:
ethyl carbamate by acylation with e
Page 109 and 110:
4.1.16. Synthesis of Ritonavir and
Page 111 and 112:
4.2. Conclusion Different important
Page 113 and 114:
Chapter 5 Stoichiometric Use of Ytt
Page 115 and 116:
The unique feature of this methodol
Page 117 and 118:
Ytterbium triflate is the most comm
Page 119 and 120:
Ruthenium(III) chloride 31.7 4 4.2
Page 121 and 122:
t-Butyl methyl ether 15 - - 82 Hexa
Page 123 and 124:
2-octanone starting material. When
Page 125 and 126:
3 Yb(OTf) 3 d 4 Ti(O i Pr) 4 e 5 B(
Page 127 and 128:
If a [1,3]-proton shift of the init
Page 129 and 130:
enhanced stereoselectivity. For exa
Page 131 and 132:
WO2006030017, 2006; c) T. C. Nugent
Page 133 and 134:
4 60 86 5 50 86 6 40 84 7 20 79 8 2
Page 135 and 136:
The reactions described above all u
Page 137 and 138:
e.g. compare entries 1, 5, 6, and 9
Page 139 and 140:
solvent in the stoichiometric and c
Page 141 and 142:
[2] Farina, V.; Grozinger, K.; Mül
Page 143 and 144:
congested which should be favored.
Page 145 and 146:
imine area % (GC analysis) time (mi
Page 147 and 148:
Inversion at the nitrogen atom of t
Page 149 and 150:
anti-6) would be expected to have m
Page 151 and 152:
e.g. AcOH, suppresses alcohol by-pr
Page 153 and 154:
eductive amination of a prochiral k
Page 155 and 156:
Appendix Experimental Section Gener
Page 157 and 158:
and the mixture was stirred for 30
Page 159 and 160:
Reaction details: Yb(OAc) 3 (1.1 eq
Page 161 and 162:
etention time [min]: major (S,S)-2b
Page 163 and 164:
time [min]: major (S,S)-2c isomer,
Page 165 and 166:
obtain the hydrochloride salt (0.41
Page 167 and 168:
with etheral HCl provided the hydro
Page 169 and 170:
Research experience: Date Project S
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Improved Methodology for the Preparation of Chiral Amines

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