N-tert-butanesulfinyl imines: Versatile intermediates for the asymmetric synthesis of amines

Accounts of Chemical Research

Volumn 35, Issue 11, 2002, Pages 984-995

  Ellman, Jonathan A ^a   Owens, Timothy D ^a   Tang, Tony P ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; AMINOALCOHOL; IMINE; N TERT BUTANESULFINYLIMINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; ASYMMETRIC SYNTHESIS; CATALYSIS; ENANTIOMER; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0036851670     PISSN: 00014842     EISSN: None     Source Type: Journal    
DOI: 10.1021/ar020066u     Document Type: Article

References (57)

1. (a) Bloch, R. Additions of organometallic reagents to C=N bonds: Reactivity and selectivity. Chem. Rev. 1998, 98, 1407-1438.
2. (b) Enders, D.; Reinhold, U. Asymmetric synthesis of amines by nucleophilic 1,2-addition of organometallic reagents to the CN-double bond. Tetrahedron: Asymmetry 1997, 8, 1895-1946.
3. (c) Kobayashi, S.; Ishitani, H. Catalytic enantioselective addition to imines. Chem. Rev. 1999, 99, 1069-1094.
4. (a) Zhou, P.; Chen, B.-C.; Davis, F. A. Syntheses and reactions of sulfinimines. In Advances in Sulfur Chemistry; Raynor, C. M., Ed.; JAI Press: Stamford, CT, 2000; Vol. 2, pp 249-282.
5. (b) Davis, F. A.; Reddy, R. E. Asymmetric synthesis using sulfinimines (thiooxime S-oxides). Phosphorus, Sulfur Silicon Relat. Elem. 1997, 120/121, 291-303.
6. Davis, F. A.; Reddy, R. E.; Szewczyk, J. M.; Reddy, G. V.; Portonovo, P. S.; Zhang, H.; Fanelli, D.; Reddy, R. T.; Zhou, P.; Carroll, P. J. Asymmetric synthesis and properties of sulfinimines (thiooxime S-oxides). J. Org. Chem. 1997, 62, 2555-2563.
7. Moreau, P.; Essiz, M.; Merour, J.-Y.; Bouzard, D. Stereoselective addition reactions to chiral N-benzylidene-p-toluenesulfinamides. Application to the synthesis of optically active 1,2-diphenylethylamines. Tetrahedron: Asymmetry 1997, 8, 591-598.
8. Liu, G.; Cogan, D. A.; Ellman, J. A. Catalytic asymmetric synthesis of tert-butanesulfinamide. Application to the asymmetric synthesis of amines. J. Am. Chem. Soc. 1997, 119, 9973-9974.
9. One report of racemic tert-butanesulfinamide 1 had appeared in a patent. Chambers, M. S.; Matassa, V. G.; Fletcher, S. R. Benzodiazepine Derivatives, Compositions Containing Them and Their Use in Therapy. U.S. Patent 5,360,802, 1994.
10. Casey, M.; Mukherjee, I.; Trabsa, H. Stereoselective additions of sulphoxides to carbonyl compounds. Tetrahedron Lett. 1992, 33, 127-130.
11. Ruano, J. L. G.; Fernandez, I.; Catalina, M.; Cruz, A. A. Asymmetric aziridination by reaction of chiral N-sulfinylimines with sulfur ylides: Stereoselective improvement by use of tert-butylsulfinyl group as chiral auxiliary. Tetrahedron: Asymmetry 1996, 7, 3407-3414.
12. Cogan, D. A.; Liu, G.; Kim, K.; Backes, B. A.; Ellman, J, A. Catalytic asymmetric oxidation of tert-butyl disulfide. Synthesis of tert-butanesulfinamides, tert-butyl sulfoxides, and tert-butanesulfinimines. J. Am. Chem. Soc. 1998, 20, 8011-8019.
13. Racemic 1 is also extremely straightforward to prepare. Reaction of tert-butyl disulfide with hydrogen peroxide followed by chlorine provides tert-butanesulfinyl chloride. Subsequent addition of ammonium hydroxide provides racemic 1 in 93% overall yield. See ref 5.
14. Liu, G.; Cogan, D. A.; Ellman, J. A. Catalytic asymmetric synthesis of tert-butanesulfinamide. Application to the asymmetric synthesis of amines. J. Am. Chem. Soc. 1997, 119, 9913-9914.
15. Liu, G.; Cogan, D. A.; Owens, T. D.; Tang, T. P.; Ellman, J. A. The synthesis of enantiomerically pure N-tert-butanesulfinyl imines (tert-butanesulfinimines) by the direct condensation of tert-butanesulfinamide with aldehydes and ketones. J. Org. Chem. 1999, 64, 1278-1284.
16. Cogan, D. A.; Ellman, J. A. The asymmetric synthesis of α,αdibranched amines by the trimethylaluminum mediated 1,2-addition of organolithiums to tert-butanesulfinyl ketimines. J. Am. Chem. Soc. 1999, 121, 268-269.
17. After our initial reports on the direct condensation of tertbutanesulfinamide 1 with aldehydes (ref 5) and ketones (ref 13), Davis reported on the direct condensation of toluenesulfinamide with carbonyl compounds. Davis, F. A.; Zhang, Y.; Andemichael, Y.; Fang, T.; Fanelli, D. L.; Zhang, H. Improved synthesis of enantiopure sulfinimines (Thiooxime S-Oxides) from p-toluenesulfinamide and aldehydes and ketones. J. Org. Chem. 1999, 64, 1403-1406.
18. Cogan, D. A.; Liu, G.; Eliman, J. A. Asymmetric synthesis of chiral amines by highly diastereoselective 1,2-additions of organometallic reagents to N-tert-butanesulfinyl imines. Tetrahedron 1999, 55, 8883-8904.
19. For recent applications of tert-butanesulfinamide chemistry to the asymmetric synthesis of diarylmethylamines, see: (a) Pflum, D. A.; Krishnamurthy, D.; Han, Z.; Wald, S. A.; Senanayake, C. H. Asymmetric synthesis of cetirizine dihydrochloride. Tetrahedron Lett. 2002, 43, 923-926. (b) Plobeck, N.; Powell, D. Asymmetric synthesis of diarylmethylamines by the diastereoselective addition of organometallic agents to chiral N-tert-butanesulfinimines: Switchover of diastereofacial selectivity. Tetrahedron: Asymmetry 2002, 13, 303-310.
20. For recent applications of tert-butanesulfinamide chemistry to the asymmetric synthesis of diarylmethylamines, see: (a) Pflum, D. A.; Krishnamurthy, D.; Han, Z.; Wald, S. A.; Senanayake, C. H. Asymmetric synthesis of cetirizine dihydrochloride. Tetrahedron Lett. 2002, 43, 923-926. (b) Plobeck, N.; Powell, D. Asymmetric synthesis of diarylmethylamines by the diastereoselective addition of organometallic agents to chiral N-tert-butanesulfinimines: Switchover of diastereofacial selectivity. Tetrahedron: Asymmetry 2002, 13, 303-310.
21. Borg, G.; Cogan, D. A.; Ellman, J. A. One-pot asymmetric reductive amination of ketones to prepare tert-butanesulfinyl protected amines. Tetrahedron Lett. 1999, 40, 6709-6712.
22. For the special case of additions to a-pyridyl-substituted ketones, see: Spero, D. M.; Kapadia, S. R. A novel method for the asymmetric synthesis of α,α-disubstituted alkylamines via grignard additions to ketimines. J. Org. Chem. 1997, 62, 5537-5541.
23. Shaw, A. W.; deSolms, S. J. Asymmetric synthesis of α,α-diaryl and α-aryl-α-heteroarylalkylamines by organometallic additions to N-tert-butanesulfinyl ketimines. Tetrahedron Lett. 2001, 42, 7173-7176.
24. Two research groups have very recently reported that either diastereomer of N-tert-butanesulfinyl diarylmethylamines may be accessed in additions of organometallic agents to tert-butanesulfinyl imines by changing the solvent or counterion and by addition of Lewis acids (see ref 16).
25. For a review on the biology and synthesis of fi-amino acids, see: Enantioselective Synthesis of β-Amino Acids; Juaristi, E., Ed.; Wiley-VCH: New York, 1997.
26. Cheng, R. P.; Gellman, S. H.; DeGrado, W. F. β-peptides: From structure to function. Chem. Rev. 2001, 101, 3219-3232.
27. Juaristi, E.; Lopez-Ruiz, H. Recent advances in the enantioselective synthesis of β-amino acids. Curr. Med. Chem. 1999, 6, 983-1004.
28. For a recent review on the synthesis of substituted β-amino acids, see: Abele, S.; Seebach, D. Preparation of achiral and of enantiopure geminally disubstituted β-amino acids for β-peptide synthesis. Eur. J. Org. Chem. 2000, 1-15.
29. Tang, T. P.; Ellman, J. A. The tert-butanesulfinyl group: An ideal chiral directing group and boc-surrogate for asymmetric β-amino acid synthesis and applications. J. Org. Chem. 1999, 64, 12-13.
30. Tang, T. P.; Ellman, J. A. Applications of N-tert-butanesulfinyl imines toward the asymmetric synthesis of β-amino acids. J. Org. Chem. 2002, 67, in press.
31. 3SnO-mediated saponification may be accomplished without racemization. In addition, PMB ester enolates may be used in place of the Me ester enolate in the initial condensation step. The PMB ester may be conveniently cleaved in the presence of the sulfinyl group by treatment with TFA in CH2CI2 (see ref 26 for details).
32. For details on the N-acylsulfonamide safety-catch linker, see: Backes, B. J.; Ellman, J. A. An alkanesulfonamide "safety-catch" linker for solid-phase synthesis. J. Org. Chem. 1999, 64, 2322-2330.
33. Davis, F. A.; McCoull, W. Concise asymmetric synthesis of α-amino acid derivatives from N-sulfinylimino esters. J. Org. Chem. 1999, 64, 3396-3397.
34. Davis, F. A.; Portonovo, P. S,; Reddy, R. E.; Chiu, Y.-H. Asymmetric strecker synthesis using enantiopure sulfinimines and diethyl aluminum cyanide: The alcohol effect. J. Org. Chem. 1996, 61, 440-441.
35. 2AICN with the corresponding toluenesulfinyl imine proceeded in similar yields and stereoselectivity, the TMSCN addition proceeded with reduced yields (77%) and stereoselectivity (83:17). As well, the authors reported that the synthesis of the p-toluenesulfinyl imine proceeded in significantly lower yield (51% versus 89%). Mabic, S.; Cordi, A. A. Synthesis of enantiomerically pure ethylenediamines from chiral sulfinimines: A new twist to the strecker reaction. Tetrahedron 2001, 57, 8861-8866.
36. Davis, F. A.; Lee, S.; Zhang, H.; Fanelli, D. L. Application of the sulfinimine-mediated asymmetric strecker synthesis to the synthesis of α-alkyl-α-amino acids. J. Org. Chem. 2000, 65, 8704-8708.
37. Borg, G.; Chino, M.; Ellman, J. A. Asymmetric synthesis of preprotected α,α-disubstituted amino acids from tert-butanesulfinyl ketimines. Tetrahedron Lett. 2001, 42, 1433-1436.
38. Sun, P.; Weinreb, S. M. tert-butylsulfonyl (Bus), a new protecting group for amines. J. Org. Chem. 1997, 62, 8604-8608.
39. (a) Prakash, G. K. S.; Mandal, M.; Olah, G. A. Stereoselective nucleophilic trifluoromethylation of N-(tert-butylsulfinyl)imines by using trimethyl(trifluoromethyl)silane. Angew. Chem., Int. Ed. 2001, 40, 589-590.
40. (b) Prakash, G. K. S.; Mandal, M.; Olah, G. A. Asymmetric synthesis of trifluoromethylated allylic amines using α,β-unsaturated N-tert-butanesulfinimines. Org. Lett. 2001, 3, 2847-2850.
41. Tang, T. P.; Volkman, S. K.; Ellman, J. A. Asymmetric synthesis of 1,2-amino alcohols using tert-butanesulfinyl aldimines and ketimines. J. Org. Chem. 2001, 66, 3707-3709.
42. Barrow, J. C.; Ngo, P. L.; Pellicore, J. M.; Selnick, H. G.; Nantermet, P. G. A facile three-step synthesis of 1,2-amino alcohols using the ellman homochiral tert-butylsulfinamide. Tetrahedron Lett. 2001, 42, 2051-2054.
43. Steinig, A. G.; Spero, D. M. Highly diastereoselective addition of grignard reagents to aliphatic, enolizable N-alkylketimines and 2,2-disubstituted 1,3-oxazolidines. Asymmetric synthesis of the antidepressant cericlamine. J. Org. Chem. 1999, 64, 2406-2410.
44. Kochi, T.; Tang, T. P.; Ellman, J. A. Asymmetric synthesis of synand anti-1,3-amino alcohols. J. Am. Chem. Soc. 2002, 124, 6518-6519.
45. Evans, D. A.; Hoveyda, A. H. Reduction of β-hydroxy ketones with catecholborane. A stereoselective approach to the synthesis of syn-1,3-diols. J. Org. Chem. 1990, 55, 5190-5192.
46. For a recent review of solid-phase linkers, see: James, I. W. Linkers for solid phase organic synthesis. Tetrahedron 1999, 55, 4855-4946.
47. Enders, D.; Kirchhoff, J. H.; Kobberling, J.; Peiffer, T. H. Asymmetric synthesis of alpha-branched primary amines on solid support via novel hydrazine resins. Org. Lett. 2001, 3, 1241-1244.
48. Dragoli, D. R.; Burdett, M. T.; Ellman, J. A. Design, synthesis, and utility of support-bound tert-butanesulfinamide. J. Am. Chem. Soc. 2001, 123, 10127-101281
49. Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds. Comprehensive Asymmetric Catalysis; Springer: New York; 1999.
50. Owens, T. D.; Hollander, F. J.; Oliver, A. G.; Ellman, J. A. Synthesis, utility, and structure of novel bis(sulfinyl)imidoamidine ligands for asymmetric Lewis acid catalysis. J. Am. Chem. Soc. 2001, 123, 1539-1540.
51. Owens, T. D.; Ellman, J. A., unpublished results.
52. Souers, A. J.; Owens, T. D.; Oliver, A. G.; Hollander, F. J.; Ellman, J. A. Synthesis and crystal structure of a unique and homochiral N,S-bonded N,N′bis(tert-butanesulfinyl)amidinate rhodium(I) complex. Inorg. Chem. 2001, 40, 5299-5301.
53. Schenkel, L.; Ellman, J. A., unpublished results.
54. (a) Evans, D. A.; Miller, S. J.; Lectka, T.; von Matt, P. Chiral bis(oxazoline)copper(II) complexes as Lewis acid catalysts for the enantioselective Diels-Alder reaction. J. Am. Chem. Soc. 1999, 121, 7559-7573.
55. Evans, D. A.; Barnes, D. M.; Johnson, J. S.; Lectka, T.; Matt, P.; Miller, S. J.; Murry, J. A.; Norcross, R. A.; Shaughnessy, E. A.; Campos K. R. Bis(oxazoline) and bis(oxazolinyl)pyridine copper complexes as enantioselective Diels-Aider catalysts: Reaction scope and synthetic applications. J. Am. Chem. Soc. 1999, 121, 7582-7594.
56. Owens, T. D.; Ellman, J. A., unpublished results.
57. Tsujimoto, T.; Ishihara, J.; Horie, M.; Murai, A. Asymmetric construction of the azaspiro[5.5]undec-8-ene system towards gymnodimine synthesis. Synlett 2002, 399-402.