메뉴 건너뛰기




Volumn 130, Issue 33, 2008, Pages 10860-10861

Finding the proton in a key intermediate of anti-markovnikov alkyne hydration by a bifunctional catalyst

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE; PROTON;

EID: 50249174451     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja803106z     Document Type: Article
Times cited : (71)

References (33)
  • 2
    • 0032558606 scopus 로고    scopus 로고
    • Reviews:(a) van den Beuken, E. K.; Feringa, B. L. Tetrahedron 1998, 54, 12985.
    • Reviews:(a) van den Beuken, E. K.; Feringa, B. L. Tetrahedron 1998, 54, 12985.
  • 16
    • 50249189306 scopus 로고    scopus 로고
    • See Supporting Information for full experimental and computational details
    • See Supporting Information for full experimental and computational details.
  • 21
    • 50249093796 scopus 로고    scopus 로고
    • 8;
    • 8;
  • 22
    • 50249140103 scopus 로고    scopus 로고
    • 6;
    • 6;
  • 23
    • 50249121152 scopus 로고    scopus 로고
    • CDCl3;
    • 3;
  • 24
    • 50249151910 scopus 로고    scopus 로고
    • 2. Of particular note, the data for complex 6 in solvents of different polarity were quite similar, consistent with an intramolecular hydrogen bond.
    • 2. Of particular note, the data for complex 6 in solvents of different polarity were quite similar, consistent with an intramolecular hydrogen bond.
  • 28
    • 50249126616 scopus 로고    scopus 로고
    • HN value is -68.6 Hz. The lower experimental magnitude (56.8 Hz) is consistent with a larger vibrationally averaged N-H separation, as zero-point motion carries the proton towards the O atom.
    • HN value is -68.6 Hz. The lower experimental magnitude (56.8 Hz) is consistent with a larger vibrationally averaged N-H separation, as zero-point motion carries the proton towards the O atom.
  • 29
    • 50249147785 scopus 로고    scopus 로고
    • 2O protons on O not N.
    • 2O protons on O not N.
  • 30
    • 50249099755 scopus 로고    scopus 로고
    • Interestingly, there is evidence of a fluxional process by which the NH proton may be transferred between the two nitrogens, perhaps via 7. As the sample of 6-(15N)2 is warmed above -80°C, the 15N peaks broaden to the point of invisibility, whereas the 1H resonance becomes more complicated between -80 and -40°C, and a triplet (J, 25.5 Hz)9a at higher temperatures. The changes in 1H spectra were modeled as a dynamic AA′X-A2X system (X, H, A, 15N, line-shape analysts giving Ea, 8 kcal mol-1 for the fluxional process.13c Similarly, the 31P signals for 6 (δ 60.7 and 51.9 ppm at -100°C8b) coalesced near -55°C
    • 8b) coalesced near -55°C
  • 31
    • 50249135423 scopus 로고    scopus 로고
    • -1 for 3 and 3-Im, respectively, consistent with a rocking motion of the two ligands.
    • -1 for 3 and 3-Im, respectively, consistent with a rocking motion of the two ligands.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.