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Volumn 351, Issue 18, 2009, Pages 3217-3234

Pyranoside phosphite-oxazoline ligand library: Highly efficient modular P,N ligands for palladium-catalyzed allylic substitution reactions. A study of the key palladium allyl intermediates

Author keywords

Allylic substitution; Asymmetric catalysis; Carbohydrate ligands; P,N ligands; Palladium

Indexed keywords


EID: 73449101484     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/adsc.200900619     Document Type: Article
Times cited : (48)

References (83)
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    • Bulky biphenyl phosphites are known to provide larger bite angles than phosphinites. The opening of the bite angle is necessary for high chiral recognition in the Pdcatalyzed alkylation reactions. See for example: a B. M. Trost, D. L. van Vranken, C. Bingel, J. Am. Chem. Soc. 1992, 114, 9327;
    • Bulky biphenyl phosphites are known to provide larger bite angles than phosphinites. The opening of the bite angle is necessary for high chiral recognition in the Pdcatalyzed alkylation reactions. See for example: a) B. M. Trost, D. L. van Vranken, C. Bingel, J. Am. Chem. Soc. 1992, 114, 9327;
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    • The flexibility offered by the biphenyl moiety can be used to fine-tune the chiral pocket formed upon complexation. Phosphite ligands have therefore proven to be highly versatile and active in Pd-catalyzed asymmetric substitution reactions, See for example a M. Dié-guez, O. Pàmies, C. Claver, J. Org. Chem. 2005, 70, 3363;
    • The flexibility offered by the biphenyl moiety can be used to fine-tune the chiral pocket formed upon complexation. Phosphite ligands have therefore proven to be highly versatile and active in Pd-catalyzed asymmetric substitution reactions, See for example a) M. Dié-guez, O. Pàmies, C. Claver, J. Org. Chem. 2005, 70, 3363;
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    • The preliminary results were partly reported in the communication: Y Mata, O. Pàmies, M. Diéguez, C. Claver, Adv. Synth. Catal. 2005, 347, 1943.
    • The preliminary results were partly reported in the communication: Y Mata, O. Pàmies, M. Diéguez, C. Claver, Adv. Synth. Catal. 2005, 347, 1943.
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    • This behavior contrasts with the effect of the oxazoline-substituent observed for related phosphinite-oxazoline ligands 1, for which enantioselectivities were higher when a methyl substituent was present
    • This behavior contrasts with the effect of the oxazoline-substituent observed for related phosphinite-oxazoline ligands 1, for which enantioselectivities were higher when a methyl substituent was present.
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    • See ref.[5e
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    • Changing the Pd catalyst concentration from 2 mol% down to 0.5 mol% has no affect on enantioselectivity.
    • Changing the Pd catalyst concentration from 2 mol% down to 0.5 mol% has no affect on enantioselectivity.
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    • For some successful applications
    • For some successful applications
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    • For some successful applications
    • For some successful applications
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    • See, for instance: a) A. Sudo, K. Saigo, J. Org. Chem. 1997, 62, 5508;
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    • In contrast to Pd-catalytic systems, Ir, Ru, W and Mo catalysts provide very high selectivity in order for the attack at the non-terminal carbon to give the chiral product
    • In contrast to Pd-catalytic systems, Ir, Ru, W and Mo catalysts provide very high selectivity in order for the attack at the non-terminal carbon to give the chiral product.
  • 66
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    • The study of the models has been performed using molecular mechanics calculations using the universal force field UFF
    • The study of the models has been performed using molecular mechanics calculations using the universal force field (UFF).
  • 70
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    • The in situ NMR studies indicate that isomers 24A and 25A react 15 and 5 times faster than isomers 24B and 25B, respectively.
    • The in situ NMR studies indicate that isomers 24A and 25A react 15 and 5 times faster than isomers 24B and 25B, respectively.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.