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Volumn 69, Issue 13, 2004, Pages 4454-4463

Stereoselective addition of α-sulfinyl carbanions to N-p-tolylsulfinylketimines: Synthesis of optically pure 1,2,2′-trialkyl-2- aminoethanols

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; CHEMICAL BONDS; LITHIUM COMPOUNDS; OXIDATION; STEREOCHEMISTRY; THERMAL EFFECTS;

EID: 3042827018     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo049666s     Document Type: Article
Times cited : (25)

References (48)
  • 1
    • 0000716787 scopus 로고
    • Schreiber, S. L., Ed.; Pergamon Press: Oxford, Chapter 1.12
    • (a) Volkmann, R. A. In Comprehensive Organic Synthesis; Schreiber, S. L., Ed.; Pergamon Press: Oxford, 1991; Vol. 1, Chapter 1.12, p 355.
    • (1991) Comprehensive Organic Synthesis , vol.1 , pp. 355
    • Volkmann, R.A.1
  • 2
    • 0001271879 scopus 로고
    • Helmechen, G., Hoffmann, R. W., Mulzer, J., Schauman, E., Eds.; Georg Thieme Verlag: Stuttgart, D.1.4
    • (b) Risch, N.; Arend, M. In Stereoselective Synthesis (Houben-Weyl); Helmechen, G., Hoffmann, R. W., Mulzer, J., Schauman, E., Eds.; Georg Thieme Verlag: Stuttgart, 1995; E21b, D.1.4, p 1833.
    • (1995) Stereoselective Synthesis (Houben-Weyl) , vol.E21B , pp. 1833
    • Risch, N.1    Arend, M.2
  • 28
  • 30
    • 0004074521 scopus 로고    scopus 로고
    • Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-Verlag: Berlin
    • (d) Comprehensive Asymmetric Catalyst; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-Verlag: Berlin, 1999.
    • (1999) Comprehensive Asymmetric Catalyst
  • 38
    • 3042833799 scopus 로고    scopus 로고
    • note
    • At 45 °C we could measure a 65% de from the NMR spectra on the crude product, but the proportion of amino sulfoxides in the mixture was lower than 60%.
  • 40
    • 3042752458 scopus 로고    scopus 로고
    • note
    • The authors have deposited atomic coordinates for 15B with the Cambridge Crystallographic Data Centre (Deposit No. 218989). The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K.
  • 42
    • 3042840729 scopus 로고    scopus 로고
    • note
    • Their NMR spectra suggested that the sulfoxides had been reduced into thioethers and the N-S bond partially hydrolyzed. These results are similar to those previously obtained from the adducts resulting from reactions of N-sulfinyl aldimines (ref 9).
  • 43
    • 3042747874 scopus 로고    scopus 로고
    • note
    • Diastereoisomers 16A and 16B differ in the configuration at sulfinylated carbon, whereas 17B and 16A have different sulfur configuration, which allows to have information about the influence of all the chiral centers.
  • 46
    • 3042752457 scopus 로고    scopus 로고
    • note
    • 3 interaction, presumably small due to the long S-O bond (see Scheme 7), the observed slightly lower reactivity of 27 is not surprising.
  • 47
    • 3042829188 scopus 로고    scopus 로고
    • note
    • To check the possible evolution through the four membered σ-sulfurane intermediates, we have prepared the N-sulfonyl aminosulfoxide 31, unable to form the six membered σ-sulfuranes, by reaction of the N-sulfonylimine derived from benzophenone with racemic methyl p-tolyl sulfoxide in the presence of LDA. The reaction of 31 with TFAA (5 equiv) and sym-collidine (4 equiv) under the same experimental conditions used for carbamates did not evolve into the amino alcohol derivative 33 but yielded the aldehyde 34, resulting in a normal Pummerer reaction. As the acidity of the NH group at 32 is higher than that of any carbamate, the fact that this substrate does not undergo the non-oxidative Pummerer reaction suggests that these reactions evolve through a six membered σ-sulfuranes as intermediates (instead of a four membered σ-sulfuranes), only possible for carbamates. However, the observed evolution for 31 could be due to the lower reactivity of the N-sulfonylamides.
  • 48
    • 0035015052 scopus 로고    scopus 로고
    • N-Sulfonylimine was prepared following the procedure described in the following reference: Ram, R. N.; Khan, A. A. Synth. Commun. 2001, 31, 841.
    • (2001) Synth. Commun. , vol.31 , pp. 841
    • Ram, R.N.1    Khan, A.A.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.