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For substitutions on another configurationally stable benzyl-type N,N-diisopropylcarbamate, see: C. Derwing, H. Frank, D. Hoppe, Eur. J. Org. Chem. 1999, 3519-3524.
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84984247528
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This compound is known in the literature. Preparation according to: a D. Hoppe, A. Brönneke, Synthesis 1982, 1045-1048;
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This compound is known in the literature. Preparation according to: a) D. Hoppe, A. Brönneke, Synthesis 1982, 1045-1048;
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34
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0000159759
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Stannane 15 in the literature: a K. Tomooka, H. Shimizu, T. Nakai, J. Organomet. Chem. 2001, 624, 364;
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37
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Preparation starting from aminoalcohols: S. E. Denmark, N. Nakajima, O. J.-C. Nicaise, A.-M. Faucher, J. P. Edwards, J. Org. Chem. 1995, 60, 4884-4892.
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-
-
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38
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0032568358
-
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3), 20% optical purity;
-
3), 20% optical purity;
-
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39
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0006342257
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compare with: b M. S. Biernbaum, H. S. Mosher, J. Org. Chem. 1971, 36, 3168-3177;
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compare with: b) M. S. Biernbaum, H. S. Mosher, J. Org. Chem. 1971, 36, 3168-3177;
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42
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54549115375
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This is in contrast to the proposed enantiodetermining step within the deprotonation stannylation sequence on benzyl carbamate 13 formulated by T. Nakai and co-workers.[15a, 19] High kinetic H/D isotope effects have been observed during the lithiation of other O-alkyl carbamates and N-Boc-allylamines (Boc, tert-butoxycarbonyl) as well: a) D. Hoppe, M. Paetow, F. Hintze, Angew. Chem. 1993, 105, 430-432;
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[15a] [19] High kinetic H/D isotope effects have been observed during the lithiation of other O-alkyl carbamates and N-Boc-allylamines (Boc = tert-butoxycarbonyl) as well: a) D. Hoppe, M. Paetow, F. Hintze, Angew. Chem. 1993, 105, 430-432;
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0009648751
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High kinetic H/D isotope effects have also been observed during the lithiation of some S-alkyl and S-benzyl thiocarbamates: a D. Reitz, P. Beak, R. Farney, L. Helmick, J. Am. Chem. Soc. 1978, 100, 5428-5436;
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34547589211
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49
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54549120795
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20 = -107.6 (c = 0.99, MeOH)): J.-R. Schwark, PhD thesis, University of Kiel (Germany), 1992.
-
20 = -107.6 (c = 0.99, MeOH)): J.-R. Schwark, PhD thesis, University of Kiel (Germany), 1992.
-
-
-
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50
-
-
54549117402
-
-
Carboxylation of alkyl lithium derivatives is known to proceed with retention of configuration. Nevertheless, inversion here fits the previous findings of our group on the carboxylation of benzyl lithium compounds; see reference [5a].
-
Carboxylation of alkyl lithium derivatives is known to proceed with retention of configuration. Nevertheless, inversion here fits the previous findings of our group on the carboxylation of benzyl lithium compounds; see reference [5a].
-
-
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51
-
-
54549120791
-
-
X-ray crystal structure analysis for (S)-21: C 21H31NO2Si, Mr, 357.56, colorless crystal, 0.35 x 0.30 x 0.25 mm3, a, 9.168(1, b, 10.949(1, c, 11.537(1) Å, β, 112.96(1)°, V, 1066.34(18) Å3, ρcalcd, 1.114 gcm -3, μ, 1.23 cm-1, empirical absorption correction (0.958 ≤ T ≤ 0.970, Z, 2, monoclinic, space group P2 1 (No. 4, λ, 0.71073 Å, T, 198 K, ω and φ scans, 9534 reflections collected (±h, ±k, ±l, sinθ)/λ, 0.67 Å-1, 4713 independent (Rint, 0.040) and 4414 observed reflections (I ≤ 2σ(I, 233 refined parameters, R1, 0.056, wR2, 0.136, Flack parameter 0.0316, max. residual electron densi
-
-3, hydrogen atoms calculated and refined as riding atoms. CCDC-657926 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre at www.ccdc.cam.ac.uk/ data_request/cif.
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Experiment: Carbamate 19 was lithiated in the presence of (-)-sparteine (11) and silylated with TMSCl (TMS=trimethylsilyl) as electrophile by employing essentially the same conditions used in the substitution sequence with chiral bis(oxazoline) 12b. Silane (-)-(S)-21 was obtained in 95% yield and with 4-6% ee.
-
Experiment: Carbamate 19 was lithiated in the presence of (-)-sparteine (11) and silylated with TMSCl (TMS=trimethylsilyl) as electrophile by employing essentially the same conditions used in the substitution sequence with chiral bis(oxazoline) 12b. Silane (-)-(S)-21 was obtained in 95% yield and with 4-6% ee.
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78
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54549112480
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ZVPE in the harmonic approximation (unscaled) as numerical derivatives of analytically calculated nuclear gradients (B97-D/SV(P, a) C. Kind, M. Reiher, J. Neugebauer, B. A. Hess, SNF Version 2.2.1, University of Erlangen, Erlangen Germany, 2002;
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