Diastereoisomeric cationic π-allylpalladium-(P,C)-MAP and MOP complexes and their relationship to stereochemical memory effects in allylic alkylation

Chemistry - A European Journal

Volumn 6, Issue 23, 2000, Pages 4348-4357

  Lloyd Jones, Guy C ^a   Stephen, Susanna C ^a   Murray, Martin ^a   Butts, Craig P ^a   Vyskočil, Štěpán ^b,c   Kočovský, Pavel ^b  

^a UNIVERSITY OF BRISTOL   (United Kingdom)

^b UNIVERSITY OF GLASGOW   (United Kingdom)

^c CHARLES UNIVERSITY   (Czech Republic)

Author keywords

Isotopic labeling; Memory effects; P,C coordination; Palladium; allyl complexes

Indexed keywords

ALLYL COMPOUND; CARBON; LIGAND; NAPHTHALENE DERIVATIVE; PALLADIUM COMPLEX;

ALKYLATION; ARTICLE; COMPLEX FORMATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STEREOCHEMISTRY;

EID: 0034404053     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3765(20001201)6:23<4348::AID-CHEM4348>3.0.CO;2-Y     Document Type: Article

References (82)

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36. These differences are reflected in the degree of pyramidalisation at ipso-C1′ (cf. valence angle Pd-C1′-C(1): 109.2° (10) and 110.5° (9)), the Pd-C1′/Pd-C2′ bond lengths: 2.34/2.47 Å (10) and 2.26/2.75 Å (9) and the Pd-C1′-C2′ angles (78° (10)/94° (9)). Only one diastereoisomer of 10 is present (albeit disordered) in the solid state. However, differences in diastereoisomer preferences between 9 and 10 in the solid state are likely to be dictated by crystal packing forces rather than by any interpretable intramolecular bias.
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60. These effects were first reported in 1996 by Trost and Bunt (see ref. [3a]), and linked to the poor performance of the ligand 16 under more conventional conditions, compared to the outstanding selectivity under optimised conditions (see ref. [23a]).
61. The origin of the memory effect, which manifests a dual and asymmetric manifold, is still a matter of debate. Asymmetric ionpairing between nucleofuge and a Pd-allyl cation in which ligand 16 is bonded through both P donors was originally suggested by Trost et al. (see ref. [3a]); see also: a) B. M. Trost, R. C. Bunt, J. Am. Chem. Soc. 1998, 120, 70-79;
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63. Negligible secondary kinetic isotope effects are observed in these reactions, see for example Table 1, entry 4.
64. "re" is global regiochemical excess (%); re (α) = 100[(α-γ)/(α + γ)].
65. These ee values are quoted in ignorance of the isotopic label, that is that which would be observed if unlabelled substrate 11 were employed. For the details of the ee determination, see the Experimental Section.
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67. 3 can sometimes act as a source of chloride, see: O. Loiseleur, P. Meier, A. Pfaltz, Angew. Chem. 1996, 108, 218-220; Angew. Chem. Int. Ed. Engl. 1996, 55, 200-202, and the results in Table 1, entry 2 could be due to the dba or the chloride.
68. mm.
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79. -.
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81. Pd] is the major diastereoisomer of [(π-cyclohexenyl)(Cl)Pd-(P)-6] (see ref. [3b]) and that this corresponds to that which would be expected in analogous complex 21, if the major diastereoisomer in solution reflects the major enantiomer of product (17) generated.
82. +.