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Volumn 351, Issue 10, 2009, Pages 1648-1670

Modular furanoside phosphite-phosphoroamidites, a readily available ligand library for asymmetric palladium-catalyzed allylic substitution reactions. Origin of enantioselectivity

Author keywords

C C coupling; Chiral pool; Furanoside phosphite phosphoroamidites; P ligands; Palladium

Indexed keywords


EID: 67650485772     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/adsc.200900073     Document Type: Article
Times cited : (34)

References (72)
  • 1
    • 0003441482 scopus 로고
    • Palladium Reagents and Catalysis
    • For reviews, see: a, Wiley, New York
    • For reviews, see: a) J. Tsuji, Palladium Reagents and Catalysis, in: Innovations in Organic Synthesis, Wiley, New York, 1995;
    • (1995) Innovations in Organic Synthesis
    • Tsuji, J.1
  • 4
    • 0000345527 scopus 로고    scopus 로고
    • Eds, E. N. Jaeobsen, A. Pfaltz, H. Yamamoto, Springer Verlag, Berlin, Chapter 24;
    • A. Pfaltz, M. Lautens, in: Comprehensive Asymmetric Catalysis, (Eds.; E. N. Jaeobsen, A. Pfaltz, H. Yamamoto), Springer Verlag, Berlin, 1999, Vol. 2, Chapter 24;
    • (1999) Comprehensive Asymmetric Catalysis , vol.2
    • Pfaltz, A.1    Lautens, M.2
  • 17
    • 15744392501 scopus 로고    scopus 로고
    • The flexibility that offers the biaryl moiety can be used to fine tune the chiral pocket formed upon complexation. See, for example: a O. Pàmies, M. Diéguez, C. Claver, J. Am. Chem. Soc. 2005, 127, 3646;
    • The flexibility that offers the biaryl moiety can be used to fine tune the chiral pocket formed upon complexation. See, for example: a) O. Pàmies, M. Diéguez, C. Claver, J. Am. Chem. Soc. 2005, 127, 3646;
  • 24
    • 33846425352 scopus 로고    scopus 로고
    • The preliminary results were partly reported in the communication: E. Raluy, C. Claver, O. Pàmies, M. Diéguez, Org. Lett. 2007, 9, 49.
    • The preliminary results were partly reported in the communication: E. Raluy, C. Claver, O. Pàmies, M. Diéguez, Org. Lett. 2007, 9, 49.
  • 33
    • 67650372719 scopus 로고    scopus 로고
    • [15] but, in our hands, this resulted in low yields.
    • [15] but, in our hands, this resulted in low yields.
  • 39
    • 33745887201 scopus 로고    scopus 로고
    • In contrast to the Pd catalytic systems, the Ir, Ru and Mo catalysts provide very high selectivity for the attack to the non-terminal carbon to give the chiral product. See, for instance: a C. Bruneau, J. L. Renaud, B. Demersemen, Chem. Eur. J. 2006, 12, 5178;
    • In contrast to the Pd catalytic systems, the Ir, Ru and Mo catalysts provide very high selectivity for the attack to the non-terminal carbon to give the chiral product. See, for instance: a) C. Bruneau, J. L. Renaud, B. Demersemen, Chem. Eur. J. 2006, 12, 5178;
  • 48
    • 0001036697 scopus 로고
    • For some more successful applications, see: a
    • For some more successful applications, see: a) B. M. Trost, R. C. Bunt, J. Am. Chem. Soc. 1994, 116, 4089;
    • (1994) J. Am. Chem. Soc , vol.116 , pp. 4089
    • Trost, B.M.1    Bunt, R.C.2
  • 52
    • 0001704975 scopus 로고    scopus 로고
    • The equilibrium between both diastereoisomers takes place via the so-called apparent π-allyl rotation, which has been shown to occur via dissociation of one of the coordinated atoms of the bidentate ligand, which allows the ligand to rotate. See: A. Gogoll, J. Örnebro, H. Grennberg, J. E. Bäckvall, J. Am. Chem. Soc. 1994, 116, 3631.
    • The equilibrium between both diastereoisomers takes place via the so-called apparent π-allyl rotation, which has been shown to occur via dissociation of one of the coordinated atoms of the bidentate ligand, which allows the ligand to rotate. See: A. Gogoll, J. Örnebro, H. Grennberg, J. E. Bäckvall, J. Am. Chem. Soc. 1994, 116, 3631.
  • 53
    • 67650428051 scopus 로고    scopus 로고
    • These results also indicate that the synlsyn A to syn /syn B interconversion should be faster than the nucleophilic attack.
    • These results also indicate that the synlsyn A to syn /syn B interconversion should be faster than the nucleophilic attack.
  • 54
    • 67650463755 scopus 로고    scopus 로고
    • The calculated diastereoisomeric excess matched the enantiomeric excess obtained experimentally for product 16
    • The calculated diastereoisomeric excess matched the enantiomeric excess obtained experimentally for product 16.
  • 55
    • 67650420014 scopus 로고    scopus 로고
    • This was confirmed by an in situ NMR study of the reactivity of the Pd intermediates with sodium malonate at low temperature. This study indicates that isomer 27A reacts around 3 times faster than isomer 27B
    • This was confirmed by an in situ NMR study of the reactivity of the Pd intermediates with sodium malonate at low temperature. This study indicates that isomer 27A reacts around 3 times faster than isomer 27B.
  • 56
    • 67650418807 scopus 로고    scopus 로고
    • The reactivity of the Pd intermediates with sodium malonate at low temperature by in situ NMR indicates that isomer 28B reacts around 20 times faster than isomer 28A.
    • The reactivity of the Pd intermediates with sodium malonate at low temperature by in situ NMR indicates that isomer 28B reacts around 20 times faster than isomer 28A.
  • 57
    • 67650442444 scopus 로고    scopus 로고
    • This is in agreement with the higher electronic differentiation between the more electrophilic allylic terminus carbon atoms of both isomers [Δ (δ13C)=4.4ppm] for complex 30 with respect to complex 29 [Δ (δ13C)=3 ppm
    • 13C)=3 ppm].
  • 71
    • 0030771619 scopus 로고    scopus 로고
    • J. P. Janssen, G. Helmchen, G. Tetrahedron Lett. 1997, 38, 8025.
    • J. P. Janssen, G. Helmchen, G. Tetrahedron Lett. 1997, 38, 8025.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.