Chapter 8 203(±)-1-(Phenyl)-2-propyn-1-ol acetate (±)-60a:Syn<strong>the</strong>tic method 7.26.1 or 7.26.2.1H-NMR (200 MHz, CDCl 3 ) δ =2.13 (s 3H), 2.67 (d 1H, J=2.29 Hz),6.43 (d 1H, J =2.29 Hz) 7.57-7.34 (m5H).13C NMR (CDCl3) δ = 20.74, 65.04, 75.04, 80.04, 127.46, 128.47,128.85, 136.25, 169.39.IR (CHCl3) ν cm-1 = 3320, 3080, 2120, 1760.GC-MS 174 M+ (100%)(±)-1-(4-Methylphenyl)-2-propyn-1-ol acetate (±)-60b:Syn<strong>the</strong>tic method 7.26.21H-NMR (200 MHz, CDCl3) δ = 2.14 (s 3H), 2.41 (s3H), 2.67 D 1H,J=2.9 HZ), 6.46 (d 1H J=2.19 Hz), 7.23 (d 2H, J=8.2 Hz), 7.46 (d2H, J=8.2 Hz).13C NMR (CDCl3) δ = 21.34, 31.01, 65.36, 75.27, 80.61, 127.83,129,52, 133.79, 139.22, 169.84.(±)-1-(4-Cyanolphenyl)-2-propyn-1-ol acetate (±)-60c:Syn<strong>the</strong>tic method 7.26.21H-NMR (200 MHz, CDCl3) δ =2.17 (s 3H), 2.73 (d 1H, J=2.28 Hz),6.51 (d 1H, J=2.28 Hz), 7.68 (d 2H J=8.40 Hz), 7.73 (d 2H J=8.40Hz).13C NMR (CDCl 3 ) δ = 31.01, 65.01, 76.84, 78.30, 111.62, 118.25,128.51, 132.79, 140.54, 169.73.(±)-1-(4Methylphenyl)-2-propyn-1-chloroacetate (±)-61b:Syn<strong>the</strong>tic method 7.27.1H-NMR (200 MHz, CDCl 3 ) δ = 2.47 (s 3H), 2.74 (s1H), 4.12 (dd2H, J=4.9 Hz, J=7.2 Hz), 6.52 (s 1H), 7.26 (d2H, J= 8.1 Hz), 7.49(d2H, J= 8.1 Hz).13C NMR (CDCl 3 ) δ = 21.38, 40.95, 67.29, 76.58, 79.88, 128.01,129.64, 132.88, 139.73, 166.31.IR (film)cm-1 = 3090, 2120, 1780, 1760, 1520.GC-MS = 218 M+ (18%), 128 (100%).MP= oil(S)-(-)-1-(4-Methylphenyl)-2-propyn-1-chloroacetate (S)-(-)-61b:Syn<strong>the</strong>tic method 7.28.2[α] 20 D - 23.3 (c 1.12, CHCl 3 ). 97.8% ee .Physical <strong>and</strong> spectral data were identical to those described below for
Chapter 8 204<strong>the</strong> racemate (±)-61 b.(±)-1-(4-Fluorophenyl)-2-propyn-1-chloroacetate (±)-61c:Syn<strong>the</strong>tic method 7.27.1H-NMR (200 MHz, CDCl 3 ) δ = 2.77 (d 1H, J= 2.25 Hz), 4.11 (dd2H, J=5.1Hz, J=10.8 Hz), 6.51 (d 1H, 2.25 Hz), 7.11 (t 2H, J=6.66Hz), 7.57 (m 2H).13C NMR (CDCl 3 ) δ = 38.94, 66.63, 76.80, 79.28, 116.06, 130.12,131.76, 145.65, 162.19, 164.67, 166.25.IR (film): ν cm-1= 3290, 2980, 2120, 1780-1740,1610.MP= oil.(S)-(-)-1-(4-Fluorophenyl)-2-propyn-1-chloroacetate (S)-(-)-61c:Syn<strong>the</strong>tic method 7.28.2[α] 20 D - 11.8 (c 1.01, CHCl 3 ). 96.8% ee .Physical <strong>and</strong> spectral data were identical to those described below for<strong>the</strong> racemate (±)-61c.(±)-1-(4-Cyanophenyl)-2-propyn-1-chloroacetate (±)-61e:Syn<strong>the</strong>tic method 7.27.1H-NMR (200 MHz, CDCl 3 ) δ = 2.80 (d 1H, J=2.34 Hz), 4.14 (m2H), 6.56 (d 1H, J=2.34 Hz), 7.70 (d 2H, J=8.11 Hz), 7.75 (d 2H,8.51 Hz).13C NMR (CDCl 3 ) δ = 40.65, 66.25, 76.84, 78.30, 113.62, 118.23,128.51, 132.80, 140.58, 166.10.IR (CHCl3): ν cm-1 = 3290, 2220, 2120, 1740,1620, 1510.MP= 61-62 °C.(S)-(-)-1-(4-Cyanophenyl)-2-propyn-1-chloroacetate (S)-(-)-61e:Syn<strong>the</strong>tic method 7.28.2[α] 20 D - 31.3 (c 0.98, CHCl 3 ). 96.6% ee .Physical <strong>and</strong> spectral data were identical to those described below for<strong>the</strong> racemate (±)-61e.(±)-1-(3-Methylphenyl)-2-propyn-1-chloroacetate (±)-61h:Syn<strong>the</strong>tic method 7.27.1H-NMR (200 MHz, CDCl 3 ) δ = 2.42 (s 3H), 2.74 (d 1H, J=2.15 Hz),4.13 (dd 2H, J= 6.6Hz; J=15.10 Hz), 6.52 (d 1H, J=2.15 Hz), 7.24 (d1H J=7.6 Hz), 7.39 (m 3H).13C NMR (CDCl 3 ) δ = 21.94, 40.94, 67.40, 76.41, 79.58, 125.05,
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Advances in the stereoselectivesynt
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ACKNOWLEDGMENT:I would like to than
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Summary:Numerous drugs are chiral,
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IndexII2.2 Synthesis of enantiopure
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IndexIV4.4. Stereochemical Assignme
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IndexVImethyl amine 69 1446.6. Stud
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IndexVIII8.23.3.1 Desilylation usin
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Chapter 1 11.Introduction1.1. Chira
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Chapter 1 3The concept of stereoche
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Chapter 1 5switches is in the area
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Chapter 1 7-bonds 9 . It is now wid
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Chapter 1 914CH 3Cyt P-450 DMOH3O 2
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Chapter 1 11piperazine) is also the
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Chapter 1 13The four stereoisomers
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Chapter 1 15single enantiomers and
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Chapter 1 17was synthesized by the
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Chapter 1 19HOHODesmolaseHOCholeste
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Chapter 1 21formic acid results in
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Chapter 1 23inactivation. 113 . Bec
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Chapter 1 25Two newer compounds whi
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Chapter 1 2715 is an advanced repre
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Chapter 1 29transformation of the a
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Chapter 1 31Enantioselective synthe
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Chapter 1 33+R,S DRUG ANCHOR R MOLE
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Chapter 1 35solubilized in hot etha
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Chapter 2 37RsORmRmRsRLRL RRRLH - A
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Chapter 2 39The stereochemistry and
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Chapter 2 41An asymmetric reducing
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Chapter 2 43This approach clearly e
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Chapter 2 45PhaxeqP 1MP 2axeqPhP 2M
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Chapter 2 47pyrrolidine ] 20 , LAH-
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Chapter 2 49Enzymatic reactions are
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Chapter 2 51As [ES] in equation 4 c
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Chapter 2 53E+AK 1AK -1AEAK 2AE+PE+
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Chapter 2 552.2.4 Lipases.Most lipa
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Chapter 2 57enzyme intermediate can
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Chapter 2 59projecting above the pl
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Chapter 2 612.3.1.1. Step 1: Adduct
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Chapter 2 63A -+ ROHRO - + AH'RO 2
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Chapter 2 65There are various effec
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Chapter 2 67The reactions were foun
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Chapter 2 69Yamanaka and coworkers
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Chapter 2 71sodium or potassium car
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Chapter 3 73The reaction is quite s
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Chapter 3 75literature as the best
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Chapter 3 77dry solvents and, is ch
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Chapter 3 79XXOH+ H 2 NDry K 2 CO 3
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Chapter 3 81substituents are the mo
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Chapter 3 83induces a rotation of t
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Chapter 3 85very sharp and it was p
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Chapter 3 87Raney NickelOH Br MeOH;
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Chapter 4 8933a-m were hydrolysed t
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Chapter 4 91benzo[b]furane (entries
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Chapter 4 93hydroxy or amine groups
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Chapter 4 95the products with ethyl
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Chapter 4 97NCO 2 HNCO 2 H(±)34c(-
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Chapter 4 99NNH37CO2EtOH(±)-27a(+)
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Chapter 4 101As already outlined ab
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Chapter 4 103(+)-(S)-2-octylimidazo
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Chapter 4 105CNNH N2 NCN nC 6 H 13N
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Chapter 4 107key step is the conver
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Chapter 4 109reverse addition in th
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Chapter 4 111which was eliminated e
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Chapter 4 113separate (±)-57a and
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Chapter 5 115to avoid this side rea
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Chapter 5 117Complete degradation o
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Chapter 5 119Entry R T °C Product
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Chapter 5 1212:1:3 in weight. All t
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Chapter 5 123reaction conditions we
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Chapter 5 125Entry Substrate R Time
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Chapter 5 127experiments. But it wa
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Chapter 5 129OClOSAM IIPH=7; R.T.OH
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Chapter 5 131OHOXHOHRHK 2 CO 3 ; Me
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Chapter 6 133HCuSO 4 .5H 2 O,NH 4 O
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Chapter 6 1356.2.1 Heteroannullatio
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Chapter 6 137This discovery allowed
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Chapter 6 139OH(±)-62OHFigure 6.1
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Chapter 6 141Entry Substrate R Time
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Chapter 6 143HOH58-a-c,e,h-lRPdCl 2
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Chapter 6 145afforded the benzo[b]f
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Chapter 6 147RR[P(Ph) 3 ]Pd°OHOPh
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Chapter 6 149H2-IodophenolOHOH(±)-
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Chapter 6 151presence of base as de
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- Page 228 and 229: Chapter 9 213References chapter 1:1
- Page 230 and 231: Chapter 9 21531) De Felice, R.; Joh
- Page 232 and 233: Chapter 9 21768) Brodie, A.M.H. in
- Page 234 and 235: Chapter 9 219112) Brodie, A. M. H.;
- Page 236 and 237: Chapter 9 2214) Karabatsos, M.C. J.
- Page 238 and 239: Chapter 9 22334c) Blow D. Nature 19
- Page 240 and 241: Chapter 9 22567a) Kundu, N.G.; Pal,
- Page 242: Chapter 9 22712) Thompson,A.S.; Hum