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Volumn 4, Issue 12, 1998, Pages 2539-2549

Memory effects in Pd-catalysed allylic alkylation: Stereochemical labelling through isotopic desymmetrization

Author keywords

Allyl complexes; Asymmetric catalysis; Isotopic labeling; P ligands; Palladium

Indexed keywords

ALLYL COMPOUND; CARBON 13; OXYGEN 18; PALLADIUM;

EID: 0031742996     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3765(19981204)4:12<2539::AID-CHEM2539>3.0.CO;2-1     Document Type: Article
Times cited : (113)

References (88)
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    • II catalyst (see for example reference [7]) to effect 1,3-allylic isomerisation (final α/γ ≈ 0.9).
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    • II can effect formal 1,3-sigmatropic rearrangement of allylic esters: a) L. E. Overman, F. M. Knoll, Tetrahedron Lett. 1979, 4, 321-324; b) T. G. Schenk, B. Bosnich, J. Am. Chem. Soc. 1985, 107, 2058-2066
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    • Isotopic perturbation of resonance may also be involved, see for example a) D. A. Forsyth, M. M. MacConnell, J. Am. Chem. Soc. 1983, 105, 5920-5921; b) J. R. Wesener, H. Günther, Tetrahedron Lett. 1982, 23, 2845-2848.
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    • For highly enantioselectivc catalysis by related Mo complexes bearing ligands related to 3 see: B. M. Trost, I. Hachiya, J. Am. Chem. Soc. 1998, 120, 1104-1105; see also D. Dvořák, I. Starý, P. Koćovský, J. Am. Chem. Soc. 1995, 117, 6130-6131.
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    • Later transition states have been suggested for asymmetric allylic alkylation, see for example: a) H. Steinhagen, M. Reggelin, G. Helmchen, Angew. Chem. 1997, 109, 2199-2202, Angew. Chem. Int. Ed. Engl. 1997, 36, 2108-2110; b) J. M. Brown, D. I. Hulmes, P. J. Guiry, Tetrahedron 1994, 50, 4493-4506.
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    • (1997) Angew. Chem. Int. Ed. Engl. , vol.36 , pp. 2108-2110
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    • supplimentary material
    • These conditions follow those reported earlier, except that racemic (±)-3 instead of enantiomerically pure (S,S)- or (R,R)-3 isused; B. M. Trost, R. C. Bunt, J. Am. Chem. Soc. 1996, 118, 235-236, supplimentary material.
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    • After turnover ceased, the concentrations of α-6 and γ-6 were invariant and thus the reactions are irreversible. Dimethylmalonate can act as a nucleofuge in allylic alkylation - although usually under more forcing conditions, see for example: a) B. M. Trost, R. C. Bunt, J. Am. Chem. Soc. 1998, 120, 70-79; b) H. Bricout, J.-F. Carpentier, A. Mortreux, Tetrahedron Lett. 1997, 38, 1053-1056.
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    • After turnover ceased, the concentrations of α-6 and γ-6 were invariant and thus the reactions are irreversible. Dimethylmalonate can act as a nucleofuge in allylic alkylation - although usually under more forcing conditions, see for example: a) B. M. Trost, R. C. Bunt, J. Am. Chem. Soc. 1998, 120, 70-79; b) H. Bricout, J.-F. Carpentier, A. Mortreux, Tetrahedron Lett. 1997, 38, 1053-1056.
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    • 18O-(±)-5b
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    • The halide is postulated to do this by acceleration of exo and endo rotamer equilibration in intermediate 1,3-diphenyl allyl Pd-(PN) complexes by one or more of the following: i) Berry pseudorotation in a pentacoordinate intermediate, ii) π-σ-π allylic equilibrium or iii) N-dissociation-rotation-coordination - see, for example, A. Gogoll, J. Örnebro, H. Grennberg, J. E. Bäckvall, J. Am. Chem. Soc. 1994, 116, 3631-3632.
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    • For substrates and nucleofuges that behave differently see: a) M. E. Krafft, A. M. Wilson, Z. Fu, M. J. Proctor, O. A. Dasse, J. Org. Chem. 1998, 63, 1748-1749; b) C. N. Farthing, P. Kočovský, J. Am. Chem. Soc. 1998, 120, 6661-6672; c) I. Starý, P. Kočovský, J. Am. Chem. Soc. 1989, 111, 4981-4982; d) I. Starý, J. Zajíček, P. Kočovský, Tetrahedron, 1992, 48, 7229-7250
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    • 1H). For all reactions except Table 2, entry 6, the ratio of [α-(S)-6 + γ-(R)-6] to [α-(R)-6+γ- (S)-6] was, within experimental error, 1:1 as predicted by a stereospecific mechanism.
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    • Very recently, it has been suggested that the ligand may act as a 'PP(O)′ ligand by one of the carbonyl oxygens acting as a third donor through a van der Waals interaction with the Pd: B. M. Trost, H. Hagelin, unpublished results cited in reference [43].
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    • 0 catalysed) to give the enantiomeric product to C-allylation.
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    • and references therein
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    • note
    • 2]- cyclopentanol, 0% de.


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