메뉴 건너뛰기




Volumn 50, Issue 21, 2011, Pages 4888-4892

Organocatalytic chemoselective monoacylation of 1,n-linear diols

Author keywords

acylation; alcohols; chemoselectivity; molecular recognition; organocatalysis

Indexed keywords

CARBON ATOMS; CHEMOSELECTIVE; CHEMOSELECTIVITY; EXCLUSIVE-OR; ORGANOCATALYSIS; ORGANOCATALYTIC;

EID: 79955759245     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201100700     Document Type: Article
Times cited : (37)

References (44)
  • 1
    • 79955756354 scopus 로고    scopus 로고
    • Imperial College Press, London.
    • P. Grunwald, Biocatalysis, Imperial College Press, London, 2009.
    • (2009) Biocatalysis
    • Grunwald, P.1
  • 19
    • 79955776433 scopus 로고    scopus 로고
    • Monofunctionlization of diols, triols and polyols using peptide-based catalysts has been reported; see
    • Monofunctionlization of diols, triols and polyols using peptide-based catalysts has been reported; see
  • 22
    • 33748581386 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2006, 45, 5616-5619
    • (2006) Angew. Chem. Int. Ed. , vol.45 , pp. 5616-5619
  • 24
    • 79955754873 scopus 로고    scopus 로고
    • Hydrogen-bonding based selectivity using peptide-based catalysts has been reported; see
    • Hydrogen-bonding based selectivity using peptide-based catalysts has been reported; see
  • 27
    • 0035800352 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2001, 40, 2824-2827.
    • (2001) Angew. Chem. Int. Ed. , vol.40 , pp. 2824-2827
  • 28
    • 85050296727 scopus 로고
    • The equation was generated by modifying an equation for the selectivity factor of kinetic resolution; see.
    • The equation was generated by modifying an equation for the selectivity factor of kinetic resolution; see:, H. B. Kagan, J. C. Fiaud, Top. Stereochem. 1988, 18, 249-331.
    • (1988) Top. Stereochem. , vol.18 , pp. 249-331
    • Kagan, H.B.1    Fiaud, J.C.2
  • 29
    • 79955770251 scopus 로고    scopus 로고
    • +=C substructure because of the reported X-ray structure of several N-acyl-4-dialkylaminopydinium ions; see
    • +=C substructure because of the reported X-ray structure of several N-acyl-4-dialkylaminopydinium ions; see
  • 35
    • 79955783179 scopus 로고    scopus 로고
    • 2-symmetry. The stereoview of the calculated structure A was shown in the Supporting Information.
    • 2-symmetry. The stereoview of the calculated structure A was shown in the Supporting Information.
  • 36
    • 79955767989 scopus 로고    scopus 로고
    • The distance between the two oxygen atoms of the extended conformation of 1,6-hexanediol is estimated to be 7.3Å by molecular modeling. The sum (10.0Å) of 7.3Å and the hydrogen-bonding distance (2.7Å) seems too long for effective molecular recognition by acylpyridinium ion A. This could be the reason of poor selectivity of monoacylation of diols such as 1,6-hexanediol and 1,7-heptanediol. In contrast, acylation of diols having a chain length shorter than five atoms proceeds with high selectivity for monoacylation. The effective distance (7.3Å) shown in Figure2 b is expected to be adjustable and therefore shortened by the bond rotation around C2-CO(NHR).
    • The distance between the two oxygen atoms of the extended conformation of 1,6-hexanediol is estimated to be 7.3Å by molecular modeling. The sum (10.0Å) of 7.3Å and the hydrogen-bonding distance (2.7Å) seems too long for effective molecular recognition by acylpyridinium ion A. This could be the reason of poor selectivity of monoacylation of diols such as 1,6-hexanediol and 1,7-heptanediol. In contrast, acylation of diols having a chain length shorter than five atoms proceeds with high selectivity for monoacylation. The effective distance (7.3Å) shown in Figure2 b is expected to be adjustable and therefore shortened by the bond rotation around C2-CO(NHR).
  • 37
    • 79955763196 scopus 로고    scopus 로고
    • The predominant formation of the monoacylate 2 a (2 a / 3 a =3.5) by DMAP-catalysis observed in entry8 in Table2 is assumed to be due to the initial low concentration of 2 a in the reaction medium and low conversion (37 % recovery of 1 a).
    • The predominant formation of the monoacylate 2 a (2 a / 3 a =3.5) by DMAP-catalysis observed in entry8 in Table2 is assumed to be due to the initial low concentration of 2 a in the reaction medium and low conversion (37 % recovery of 1 a).
  • 38
    • 79955770037 scopus 로고    scopus 로고
    • Specific rate acceleration in acylation by peptide-based catalysts has been reported; see
    • Specific rate acceleration in acylation by peptide-based catalysts has been reported; see
  • 41
    • 79955783594 scopus 로고    scopus 로고
    • Direct monoacylation of linear diols may be useful in the preparation of insect pheromones and hybrid esters, see
    • Direct monoacylation of linear diols may be useful in the preparation of insect pheromones and hybrid esters, see
  • 44
    • 79955748672 scopus 로고    scopus 로고
    • reference[3a].
    • reference[3a].


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.