Improved Methodology for the Preparation of Chiral Amines

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[28] H. B. Kagan, J. C. Fiaud, Topics in Stereochemistry, E. L. Eliel and S. H. Wilen (Eds.) Vol. 18, Wiley, New York, 1988, pp. 249. [29] Y. Kim, E. T. Choi, M. H. Lee, Y. S. Park, Tetrahedron Lett. 2007, 48, 2833. [30] J. B. Crawford, R. T. Skerlj, G. J. Bridger, J. Org. Chem., 2007, 72, 669. [31] R. Noyori, T. Ikeda, T. Ohkuma, M. Widhalm, M. Kitamura, H. Takaya, S. Akutagawa, N. Sayo, T. Saito, J. Am. Chem. Soc. 1989, 111, 9134. [32] V. Sunjic, F. Kajfez, I. Stromar, N. Blazevic, D. Kolbah, J. Heterocycl. Chem. 1973, 10, 591. [33] Z. -Y. Wei, E. E. Knaus, Tetrahedron 1994, 50, 5569. [34] R. M. Scott, G. D. Armitage, E. Haddock, Optically active 4-phenoxyphenoxypropionic acid derivatives (Shell Internationale Research Maatschappij B. V., Neth.) 1980, 2, 946, 652, pp. 23. [35] A. G. Myers, B. H. Yang, H. Chen, J. L. Gleason, J. Am. Chem. Soc. 1994, 116, 9361. [36] W. S. Knowles, M. J. Sabacky, B. D. Vineyard, D. J. Weinkauf, J. Am. Chem. Soc. 1975, 97, 2567; b) W. S. Knowles, Angew. Chem. Int. Ed. 2002, 41, 1998. [37] R. Noyori, Adv. Synth. Catal. 2003, 345, 15. [38] a) T. Ohta, H. Takaya, M. Kitamura, K. Nagai, R. Noyori, J. Org. Chem. 1987, 52, 3174; b) M. Kitamura, M. Yoshimura, M. Tsukamoto, R. Noyori, Enantiomer 1996, 1, 281. [39] For other synthetic applications, see reviews: a) G. M. Ramos Tombo, G. Bellus, Angew. Chem. Int. Ed. Engl. 1991, 30, 1193; b) A. Börner, J. Holz in Transition Metals for Organic Synthesis, Vol. 2 (Eds.: M. Beller, C. Bolm), Wiley- VCH, Weinheim, 1998, pp.3; c) J. M. Brown in Comprehensive Asymmetric Catalysis, Vol. 1 (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, Berlin, 1999, pp. 121; d) T. Ohkuma, M. Kitamura, R. Noyori in Catalytic Asymmetric Synthesis, 2nd ed. (Ed.: I. Ojima), Wiley-VCH, New York, 2000. [40] a) M. Kitamura, M. Tokunaga, T. Ohkuma, R. Noyori, Tetrahedron Lett. 1991, 32, 4163; b) M. Kitamura, M. Tokunaga, T. Ohkuma, R. Noyori, Org. Synth. 1993, 71, 1; c) K. Mashima, K. Kusano, N. Sato, Y. Matsumura, K. Nozaki, H. Kumobayashi, N. Sayo, Y. Hori, T. Ishizaki, S. Akutagawa, H. Takaya, J. Org. Chem. 1994, 59, 3064. [41] a)T. Katsuki, K. B. Sharpless, J. Am. Chem. Soc. 1980, 102, 5974; b) R. M. Hanson, K. B. Sharpless (1986) J. Org. Chem. 1986, 51,1922; c) E. N. Jacobsen, I. Marko , W. S. Mungall, G. Schröder, K. B. Sharpless, (1988) J. Am. Chem. Soc. 1988,110, 1968; d) G. Li, H. T. Chang, K. B. Sharpless, Angew. Chem. Int. Ed. 1996, 35, 451; e) R. A. Johnson, K. B. Sharpless, in Catalytic Asymmetric Synthesis (Ed.: I. Ojima) VCH, Weinheim, 1993. 30
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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 and 8: Prof. Mohamed El-Azizi, Prof. Abdel
Page 9 and 10: Et EtOH EtOAc GC h HPLC HRMS Hz J K
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: [8] E. L. Eliel, S. H. Wilen, Stere
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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