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For some selected recent reviews, see: [1a] M. F. Semmelhack in Comprehensive Organometallic Chemistry II, vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, pp. 979-1015. [1b] M. F. Semmelhack in Comprehensive Organometallic Chemistry II, vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, pp. 1017-1038. [1c] S. G. Davies, T. D. McCarthy in Comprehensive Organometallic Chemistry II, vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, pp. 1039-1070. [1d] L. S. Hegedus, Transition Metals in the Synthesis of Complex Organic Molecules, University Science Books, Mill Valley, 1994, chapter 10.
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For some selected recent reviews, see: [1a] M. F. Semmelhack in Comprehensive Organometallic Chemistry II, vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, pp. 979-1015. [1b] M. F. Semmelhack in Comprehensive Organometallic Chemistry II, vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, pp. 1017-1038. [1c] S. G. Davies, T. D. McCarthy in Comprehensive Organometallic Chemistry II, vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, pp. 1039-1070. [1d] L. S. Hegedus, Transition Metals in the Synthesis of Complex Organic Molecules, University Science Books, Mill Valley, 1994, chapter 10.
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For some selected recent reviews, see: [1a] M. F. Semmelhack in Comprehensive Organometallic Chemistry II, vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, pp. 979-1015. [1b] M. F. Semmelhack in Comprehensive Organometallic Chemistry II, vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, pp. 1017-1038. [1c] S. G. Davies, T. D. McCarthy in Comprehensive Organometallic Chemistry II, vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, pp. 1039-1070. [1d] L. S. Hegedus, Transition Metals in the Synthesis of Complex Organic Molecules, University Science Books, Mill Valley, 1994, chapter 10.
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For some selected recent reviews, see: [1a] M. F. Semmelhack in Comprehensive Organometallic Chemistry II, vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, pp. 979-1015. [1b] M. F. Semmelhack in Comprehensive Organometallic Chemistry II, vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, pp. 1017-1038. [1c] S. G. Davies, T. D. McCarthy in Comprehensive Organometallic Chemistry II, vol. 12 (Eds.: E. W. Abel, F. G. A. Stone, G. Wilkinson), Pergamon, Oxford, 1995, pp. 1039-1070. [1d] L. S. Hegedus, Transition Metals in the Synthesis of Complex Organic Molecules, University Science Books, Mill Valley, 1994, chapter 10.
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3 complexes, there is a para-directing effect of electron-withdrawing groups and a meia-directing effect of donor substituents. See, for example: [6a] G. Jaouen, S. Top, A. Laconi, D. Couturier, J. Brocard, J. Am. Chem. Soc. 1984, 106, 2207. [6b] J. Brocard, A. Laconi, D. Couturier, S. Top, G. Jaouen, J. Chem. Soc., Chem. Commun. 1984, 475. [6c] J. Brocard, L. Pelinski, J. Lebibi, J Organomet. Chem. 1986, 309, 299. [6d] J. Brocard, J. Lebibi, J. Organomet. Chem. 1987, 320, 295. [6e] J. Lebibi, L. Pelinski, J. Brocard, Tetrahedron 1990, 46, 6011.
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20
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37049109172
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3 complexes, there is a para-directing effect of electron-withdrawing groups and a meia-directing effect of donor substituents. See, for example: [6a] G. Jaouen, S. Top, A. Laconi, D. Couturier, J. Brocard, J. Am. Chem. Soc. 1984, 106, 2207. [6b] J. Brocard, A. Laconi, D. Couturier, S. Top, G. Jaouen, J. Chem. Soc., Chem. Commun. 1984, 475. [6c] J. Brocard, L. Pelinski, J. Lebibi, J Organomet. Chem. 1986, 309, 299. [6d] J. Brocard, J. Lebibi, J. Organomet. Chem. 1987, 320, 295. [6e] J. Lebibi, L. Pelinski, J. Brocard, Tetrahedron 1990, 46, 6011.
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3 complexes, there is a para-directing effect of electron-withdrawing groups and a meia-directing effect of donor substituents. See, for example: [6a] G. Jaouen, S. Top, A. Laconi, D. Couturier, J. Brocard, J. Am. Chem. Soc. 1984, 106, 2207. [6b] J. Brocard, A. Laconi, D. Couturier, S. Top, G. Jaouen, J. Chem. Soc., Chem. Commun. 1984, 475. [6c] J. Brocard, L. Pelinski, J. Lebibi, J Organomet. Chem. 1986, 309, 299. [6d] J. Brocard, J. Lebibi, J. Organomet. Chem. 1987, 320, 295. [6e] J. Lebibi, L. Pelinski, J. Brocard, Tetrahedron 1990, 46, 6011.
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3 complexes, there is a para-directing effect of electron-withdrawing groups and a meia-directing effect of donor substituents. See, for example: [6a] G. Jaouen, S. Top, A. Laconi, D. Couturier, J. Brocard, J. Am. Chem. Soc. 1984, 106, 2207. [6b] J. Brocard, A. Laconi, D. Couturier, S. Top, G. Jaouen, J. Chem. Soc., Chem. Commun. 1984, 475. [6c] J. Brocard, L. Pelinski, J. Lebibi, J Organomet. Chem. 1986, 309, 299. [6d] J. Brocard, J. Lebibi, J. Organomet. Chem. 1987, 320, 295. [6e] J. Lebibi, L. Pelinski, J. Brocard, Tetrahedron 1990, 46, 6011.
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3 complexes, there is a para-directing effect of electron-withdrawing groups and a meia-directing effect of donor substituents. See, for example: [6a] G. Jaouen, S. Top, A. Laconi, D. Couturier, J. Brocard, J. Am. Chem. Soc. 1984, 106, 2207. [6b] J. Brocard, A. Laconi, D. Couturier, S. Top, G. Jaouen, J. Chem. Soc., Chem. Commun. 1984, 475. [6c] J. Brocard, L. Pelinski, J. Lebibi, J Organomet. Chem. 1986, 309, 299. [6d] J. Brocard, J. Lebibi, J. Organomet. Chem. 1987, 320, 295. [6e] J. Lebibi, L. Pelinski, J. Brocard, Tetrahedron 1990, 46, 6011.
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J. Blagg, S. G. Davies, C. L. Goodfellow, K. H. Sutton, J. Chem. Soc., Perkin Trans, I 1987, 1805. The term "complex-induced proximity effect" was coined by Beak and Meyers: P. Beak, A. I. Meyers, Ace. Chem. Res. 1986, 19, 356.
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J. Blagg, S. G. Davies, C. L. Goodfellow, K. H. Sutton, J. Chem. Soc., Perkin Trans, I 1987, 1805. The term "complex-induced proximity effect" was coined by Beak and Meyers: P. Beak, A. I. Meyers, Ace. Chem. Res. 1986, 19, 356.
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The lithiated species can be assumed to possess a structure 3, in which the deprotonated center is part of a newly formed double bond (see refs.[1c][2]). In analogy to the deprotonation of ketones, the C-H bond to be broken during the deprotonation step should, for stereoelectronic reasons, be as close to parallel as possible in relation to the aryl π orbitals, so that the developing p orbital can be stabuzed early. For related discussions, see, for instance: [8a] P. Deslongchamps, Stereoelectronic Effects in Organic Chemistry, Pergamon, Oxford, 1983, pp. 243-267. and references cited therein. [8b] K. Seemeyer, R. H. Hertwig, J. Hrusák, W. Koch, H. Schwarz, Organometallics 1995, 14, 4409.
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The lithiated species can be assumed to possess a structure 3, in which the deprotonated center is part of a newly formed double bond (see refs.[1c][2]). In analogy to the deprotonation of ketones, the C-H bond to be broken during the deprotonation step should, for stereoelectronic reasons, be as close to parallel as possible in relation to the aryl π orbitals, so that the developing p orbital can be stabuzed early. For related discussions, see, for instance: [8a] P. Deslongchamps, Stereoelectronic Effects in Organic Chemistry, Pergamon, Oxford, 1983, pp. 243-267. and references cited therein. [8b] K. Seemeyer, R. H. Hertwig, J. Hrusák, W. Koch, H. Schwarz, Organometallics 1995, 14, 4409.
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85163229575
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note
-
It should be noted that mild conditions (0°C) are required to achieve a reasonably high yield. At higher temperatures, an increased formation of by-products was observed and the isolated yield of rac-20 dropped, for instance, to 32% when the reaction was performed at 40°C. Addition of HMPA, which is reported to give improved yields in some comparable cases[15], resulted only in a decreased yield of rac-20 (ca. 30% at 0°C).
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51
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0001168999
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For some early examples for the use of dimenthyl fumarate in asymmetric Diels-Alder reactions, see: [20a] H. M. Walborsky, L. Barash, T. C. Davis, J. Org. Chem. 1961, 26, 4778. [20b] H. M Walborsky, L. Barash, T. C. Davis, Tetrahedron 1963, 19, 2333. [20c] J. Sauer, J. Kredel, Angew. Chem. 1965, 77, 1037. [20d] J. Sauer, J. Kredel, Tetrahedron 1966, 22, 6359.
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For some early examples for the use of dimenthyl fumarate in asymmetric Diels-Alder reactions, see: [20a] H. M. Walborsky, L. Barash, T. C. Davis, J. Org. Chem. 1961, 26, 4778. [20b] H. M Walborsky, L. Barash, T. C. Davis, Tetrahedron 1963, 19, 2333. [20c] J. Sauer, J. Kredel, Angew. Chem. 1965, 77, 1037. [20d] J. Sauer, J. Kredel, Tetrahedron 1966, 22, 6359.
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For some early examples for the use of dimenthyl fumarate in asymmetric Diels-Alder reactions, see: [20a] H. M. Walborsky, L. Barash, T. C. Davis, J. Org. Chem. 1961, 26, 4778. [20b] H. M Walborsky, L. Barash, T. C. Davis, Tetrahedron 1963, 19, 2333. [20c] J. Sauer, J. Kredel, Angew. Chem. 1965, 77, 1037. [20d] J. Sauer, J. Kredel, Tetrahedron 1966, 22, 6359.
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57
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85163234370
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-
-1, λ = 254 nm, retention time for 21: 15.54 min; retention time for ent21: 14.10 min.
-
-1, λ = 254 nm, retention time for 21: 15.54 min; retention time for ent21: 14.10 min.
-
-
-
-
60
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0000315424
-
-
(Eds.: B. M. Trost, T. Fleming), Pergamon, Oxford
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For some reviews on radical cyclizations, see: [24a] D. P. Curran, in Comprehensive Organic Synthesis, vol. 4 (Eds.: B. M. Trost, T. Fleming), Pergamon, Oxford, 1991, pp. 779-831. [24b] C. P. Jasperse, D. P. Curran, T. L. Fervig, Chem. Rev. 1991, 91, 1237.
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Curran, D.P.1
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For some reviews on radical cyclizations, see: [24a] D. P. Curran, in Comprehensive Organic Synthesis, vol. 4 (Eds.: B. M. Trost, T. Fleming), Pergamon, Oxford, 1991, pp. 779-831. [24b] C. P. Jasperse, D. P. Curran, T. L. Fervig, Chem. Rev. 1991, 91, 1237.
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Jasperse, C.P.1
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Fervig, T.L.3
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62
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85163227414
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note
-
In our hands, the yield of rac-13 was only 29% (ref.[12]: 79%) after chromatography and recrystallization. The melting point of the our material (64°C), however, was found to exceed that given in the literature (53°C)[12].
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-
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66
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0028330334
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[28b] J. A. Casalnuovo, R. W. Scott, E. A. Harwood, N. E. Schore, Tetrahedron Lett. 1994, 35, 1153.
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Casalnuovo, J.A.1
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67
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85163233180
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-
note
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-3.
-
-
-
-
68
-
-
85163223413
-
-
note
-
-3.
-
-
-
-
69
-
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85163235476
-
-
note
-
-3.
-
-
-
-
70
-
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85163228405
-
-
note
-
-3. -Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-101004. Copies of the data can be obtained free of charge on application to CCDC. 12 Union Road, Cambridge CB2 1EZ. UK [Fax: int. code + 44(1223)336-033; E-mail: deposit@ccdc.cam.ac.uk].
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71
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85163223905
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W. P. Aue, E. Bartholdi, R. R. Ernst, J. Magn. Reson. 1977, 28, 542.
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Aue, W.P.1
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Ernst, R.R.3
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72
-
-
85163231028
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-
unpublished results
-
Complex rac-1 was prepared as described in ref.[5]; complex 50 was obtained from 6,7-dimethoxytetralin by complexation and disilylation: H.-G. Schmalz, A. Schwarz, unpublished results.
-
-
-
Schmalz, H.-G.1
Schwarz, A.2
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73
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-
85163224433
-
-
note
-
6]DMSO conditions (lower temperatures and/or shorter reaction times) failed.
-
-
-
-
74
-
-
85163228697
-
-
note
-
The degree of deuteration (and the level of inaccuracy) was determined (estimated) by comparison with the integrals observed for the methoxy or the TMS groups.
-
-
-
-
75
-
-
85163228430
-
-
note
-
The fact that no significant loss of regioselectivity was found in these experiments indicates that the inherent directing effect must be stronger than the primary kinetic isotope effect.
-
-
-
-
76
-
-
85163234379
-
-
note
-
A protonation at the chromium atom of the anionic intermediate, which would eventually have resulted in the formation of an endo-protonated complex could thereby be excluded.
-
-
-
-
77
-
-
85163233163
-
-
note
-
-3. Further details of the crystal structure investigations are available on request from the CCDC; for details see ref. [29d].
-
-
-
-
78
-
-
85163228336
-
-
note
-
The formation of benzylic alkylation products derived from rac-7 was established by NMR of the crude product mixture but purification was not successful due to rapid decomposition.
-
-
-
-
79
-
-
85163224289
-
-
note
-
Brocard and Lebibi (ref.[6d]) summarize their experiments: "The regiospecificity of the benzylic functional group of arenetricarbonylchromium cannot be explained by preferential attack at the carbon which is eclipsed by the chromium-carbonyl bond. Electronic effects in directing the regiospecificity of benzylic attack were found to predominate."
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-
-
-
80
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0001562295
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85163228641
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This representation is favorable due to the experimental fact that the anions possess a high configurative stability; see, for instance: S. E. Gibson, M. J. Schneider, M. H. Smith, J. Chem Soc., Chem. Commun. 1996, 839. Our own NMR data of some lithiated species (see: T. Volk, Dissertation, TU Berlin, 1996) support this picture.
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Gibson, S.E.1
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99
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85163224507
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Dissertation, TU Berlin
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This representation is favorable due to the experimental fact that the anions possess a high configurative stability; see, for instance: S. E. Gibson, M. J. Schneider, M. H. Smith, J. Chem Soc., Chem. Commun. 1996, 839. Our own NMR data of some lithiated species (see: T. Volk, Dissertation, TU Berlin, 1996) support this picture.
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(1996)
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-
Volk, T.1
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100
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-
33847089848
-
-
3Si) and that the arene ligand carbon atoms which are eclipsed with a CO ligand are predicted to be more electrophilic (see: refs. [1a][40][41], as well as: T. A. Albright, P. Hofmann, R. Hoffmann, J. Am. Chem. Soc. 1977, 99, 7546).
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Albright, T.A.1
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0007252545
-
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-1 in the case of highly substituted systems. For a review, see: [47a] M. J. McGlinchey, Adv. Organomet. Chem. 1992, 34, 285. See also: [47b] K. V. Kilway, J. S. Siegel, J. Am. Chem. Soc 1992, 114, 255; and references cited therein.
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McGlinchey, M.J.1
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102
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0000800611
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and references cited therein
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-1 in the case of highly substituted systems. For a review, see: [47a] M. J. McGlinchey, Adv. Organomet. Chem. 1992, 34, 285. See also: [47b] K. V. Kilway, J. S. Siegel, J. Am. Chem. Soc 1992, 114, 255; and references cited therein.
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Kilway, K.V.1
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105
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0003887404
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Harper Collins, New York, and references cited therein
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See, for instance: T. H. Lowry, K. S. Richardson, Mechanism and Structure in Organic Chemistry, Harper Collins, New York, 1987, p. 205; and references cited therein.
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Mechanism and Structure in Organic Chemistry
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Lowry, T.H.1
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Henderson, R.A.1
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R. A. Henderson, Angew. Chem. 1996, 108, 1024; Angew. Chem. Int. Ed. Engl. 1996, 35, 946.
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108
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85163228349
-
-
note
-
6.
-
-
-
-
109
-
-
85163229440
-
-
note
-
After decomplexation, the isomers could be unambiguously assigned by NOE experiments (see Experimental Section).
-
-
-
-
111
-
-
2142653131
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[54a] L. Fisnerova, B. Kakac, O. Nemecek, A. Simek, Z. J Vejdelek, Collect. C=ech. Chem. Commun. 1967, 32, 4082.
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H.-G. Schmalz; B. Millies, J. W. Bats, G. Dürner, Angew. Chem. 1992, 104, 640; Angew. Chem. Int Ed. Engl. 1992, 31, 631; and refs. cited therein.
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119
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85163227129
-
-
For the assignments of the benzylic protons, see Table 2
-
For the assignments of the benzylic protons, see Table 2.
-
-
-
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