C2-symmetric planar chiral ferrocene diamides by (-)-sparteine-mediated directed ortfto-lithiation. Synthesis and catalytic activity

Organic Letters

Volumn 2, Issue 5, 2000, Pages 629-631

  Laufer, Radoslaw S ^a   Veith, Ulrich ^a,b   Taylor, Nicholas J ^a   Snieckus, Victor ^a  

^a UNIVERSITY OF WATERLOO   (Canada)

^b LONZA AG   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000769340     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol991381s     Document Type: Article

References (49)

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22. An asymmetric hydrogenation in the synthesis of (+)-biotin by Lonza: McGarrity, J.; Spindler, F.; Fuchs, R.; Eyer, M. (LONZA AG), EP-A 624 587-A2,1995; Chem. Abstr. 1995, 122, P81369q. Togni, A. Angew. Chem., Int. Ed. Engl. 1996, 35, 1475. Ciba-Geigy AG (Novartis) multiton synthesis of the herbicide (S)-Metolachlor: Spiendler, F.; Pugin, B.; Jalett, H.-P.; Buser, H.-P.; Pittelkow, W.; Blasser, H.-U. In Catalysis of Organic Reactions; Malz, R. E., Ed.; Marcel Dekker: New York, 1996, p 153. Spiendler, F.; Pugin, B. (Ciba-Geigy AG), EP-A 0 256982, 1988; Chem. Abstr. 1990, 112, 138725c.
23. An asymmetric hydrogenation in the synthesis of (+)-biotin by Lonza: McGarrity, J.; Spindler, F.; Fuchs, R.; Eyer, M. (LONZA AG), EP-A 624 587-A2,1995; Chem. Abstr. 1995, 122, P81369q. Togni, A. Angew. Chem., Int. Ed. Engl. 1996, 35, 1475. Ciba-Geigy AG (Novartis) multiton synthesis of the herbicide (S)-Metolachlor: Spiendler, F.; Pugin, B.; Jalett, H.-P.; Buser, H.-P.; Pittelkow, W.; Blasser, H.-U. In Catalysis of Organic Reactions; Malz, R. E., Ed.; Marcel Dekker: New York, 1996, p 153. Spiendler, F.; Pugin, B. (Ciba-Geigy AG), EP-A 0 256982, 1988; Chem. Abstr. 1990, 112, 138725c.
24. An asymmetric hydrogenation in the synthesis of (+)-biotin by Lonza: McGarrity, J.; Spindler, F.; Fuchs, R.; Eyer, M. (LONZA AG), EP-A 624 587-A2,1995; Chem. Abstr. 1995, 122, P81369q. Togni, A. Angew. Chem., Int. Ed. Engl. 1996, 35, 1475. Ciba-Geigy AG (Novartis) multiton synthesis of the herbicide (S)-Metolachlor: Spiendler, F.; Pugin, B.; Jalett, H.-P.; Buser, H.-P.; Pittelkow, W.; Blasser, H.-U. In Catalysis of Organic Reactions; Malz, R. E., Ed.; Marcel Dekker: New York, 1996, p 153. Spiendler, F.; Pugin, B. (Ciba-Geigy AG), EP-A 0 256982, 1988; Chem. Abstr. 1990, 112, 138725c.
25. 2O/hexane).
26. 2Cl (4a) 49% yleid, meso:dl = >95:<5) (For other data, see Laufer, R. M.Sc. Thesis, University of Waterloo, 1998).
27. Notably, n-BuLi·2 is capable of effecting a double deprotonation of 1 but only in the presence of TMSCl as the electrophilic partner (e.g. in PhMe 71% yield of 4b, dl:meso = 72:28, 97% op (Laufer, R. M.Sc. Thesis, University of Waterloo, 1998).
28. w, and GOF (for 5445 data with F > 6.0σ(F)) of 0.0238, 0.0272, and 2.05, respectively, for solution using the (S) model. The corresponding values for solution of the (R) model were 0.0433, 0.0492, and 3.70.
29. 3N for diphenylphosphine derivative 3f). Diphenylphosphine derivatives 3f and 4a were found to be air-sensitive but could be stored indefinitely as solids under argon at -20 °C.
30. Toluene offers greatly improved solubility of ferrocenyldiamide 1. The opposite solvent effect was observed in (-)-sparteine-assisted DoM of N,N-diisopropylferrocenecarboxamide (ref 4).
31. 1/2 ≈ 9 h at rt (either in 90:10 or 98:2 hexane:i-PrOH).
32. Quesnelle, C. A.; Familioni, O. B.; Snieckus, V. Synlett 1994, 349 and references therein.
33. 3/DME/85 °C/5 d.
34. 2(dppf)/CuO/DMF/150 °C/18 h; Gronowitz, S.; Bjork, P.; Malm, J.; Hornfeldt, A.-B. J. Organomet. Chem. 1993, 460, 127.
35. Alo, B. I.; Kandil, A.; Patil, P. A.; Sharp, M. J.; Siddiqui, M. A.; Snieckus, V. J. Org. Chem. 1991, 56, 3763.
36. Ee for 31 was not determined because of availability of only an approximate value for ee of the ferrocenyltin 3e.
37. Beak, P.; Kerrick, S. T.; Wu, S.; Chu, J. J. Am. Chem. Soc. 1994, 116, 3231.
38. Typical procedure is analogous to that used for the monometalation of 1 (ref 14)
39. 1/2 > 40 d at rt (90:10 hexane:i-PrOH).
40. For reviews on catalyzed allylic substitution reactions, see: (a) Trost, B. M.; Van Vranken, D. L. Chem. Rev. 1996, 96, 395.
41. (b) Trost, B. M. Acc. Chem. Res. 1996, 29, 355.
42. (c) Helmchen, G. J. Organomet. Chem. 1999, 576, 203.
43. Trost, B. M.; Murphy, D. J. Organometallics 1985, 4, 1143.
44. D +15.9 (c 0.71, EtOH).
45. Noyori, R. Asymmetric catalysis in organic synthesis; Wiley: New York, 1994.
46. R 27.20 and 29.66 min).
47. (b) For the value of the optical rotation, see: Packard, R. H.; Kenyon, J. J. Chem. Soc. 1914, 1115. Also see: Kitamura, M.; Suga, S.: Kawai, K.; Noyori, R. J. Am. Chem. Soc. 1986, 108, 6071.
48. (b) For the value of the optical rotation, see: Packard, R. H.; Kenyon, J. J. Chem. Soc. 1914, 1115. Also see: Kitamura, M.; Suga, S.: Kawai, K.; Noyori, R. J. Am. Chem. Soc. 1986, 108, 6071.
49. Quite unusual and, to our knowledge, previously unobserved is the variation in the enatiotopicity of the reaction as a function of the solvent (entry 1 vs entry 2) and use of lithium salt of carbinol 3c (entry 2 vs entry 3). We currently do not have an explanation for this observation.