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1
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0042379988
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For a very recent review see
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For a very recent review see: B.M. Trost, M.L. Crawley, Chem. Rev. 103 (2003) 2921.
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(2003)
Chem. Rev.
, vol.103
, pp. 2921
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Trost, B.M.1
Crawley, M.L.2
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5
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0000390005
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2-Pd-p[C(3)=C(2)]-C(1) or η2-Pd-p-[C(1)=C(2)]-C(3) alkene complex respectively. For discussions see
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2-Pd-p[C(3)=C(2)]-C(1) or η2-Pd-p-[C(1)=C(2)]-C(3) alkene complex respectively. For discussions see: A. Pfaltz, Acta Chem. Scand. 50 (1996) 189
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(1996)
Acta Chem. Scand.
, vol.50
, pp. 189
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Pfaltz, A.1
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28
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0037768557
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Kočovský P. Vyskočil Š. Císařová I. Sejbal J. Tišlerová I. Smrčina M. Lloyd-Jones G.C. Stephen S.C. Butts C.P. Murray M. Langer V. J. Am. Chem. Soc. 121 1999 7714
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(1999)
J. Am. Chem. Soc.
, vol.121
, pp. 7714
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Kočovský, P.1
Vyskočil, Š.2
Císařová, I.3
Sejbal, J.4
Tišlerová, I.5
Smrčina, M.6
Lloyd-Jones, G.C.7
Stephen, S.C.8
Butts, C.P.9
Murray, M.10
Langer, V.11
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29
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3042544299
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In press
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G.C. Lloyd-Jones, S.C. Stephen, I.J.S. Fairlamb, A. Martorell, B. Dominguez, P.M. Tomlin, M. Murray, J.M. Fernandez, J.C. Jeffery, T. Riis-Johannessen, T. Guerziz, Pure App. Chem. (2003) 75, in press.
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(2003)
Pure App. Chem.
, pp. 75
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Lloyd-Jones, G.C.1
Stephen, S.C.2
Fairlamb, I.J.S.3
Martorell, A.4
Dominguez, B.5
Tomlin, P.M.6
Murray, M.7
Fernandez, J.M.8
Jeffery, J.C.9
Riis-Johannessen, T.10
Guerziz, T.11
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33
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0035116074
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2Pd(Cl)(σ-allyl) in which the phosphines could attain a trans-relationship
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2Pd(Cl)(σ-allyl) in which the phosphines could attain a trans-relationship: C. Amatore, A. Jutand, M.A. M'Barki, G. Meyer, L. Mottier, Eur. J. Inorg. Chem. (2001) 873.
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(2001)
Eur. J. Inorg. Chem.
, pp. 873
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Amatore, C.1
Jutand, A.2
M'Barki, M.A.3
Meyer, G.4
Mottier, L.5
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35
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0033610498
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In the case of non-allylic intermediates, and in particular with Ni, interactions of type III have been cited as important factors in control of reactivity and selectivity through ligand hemilability. Interactions of type II may have been overlooked, see:
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In the case of non-allylic intermediates, and in particular with Ni, interactions of type III have been cited as important factors in control of reactivity and selectivity through ligand hemilability. Interactions of type II may have been overlooked, see: Nandi M. Jin J. RajanBabu T.V. J. Am. Chem. Soc. 121 1999 9899
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(1999)
J. Am. Chem. Soc.
, vol.121
, pp. 9899
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Nandi, M.1
Jin, J.2
RajanBabu, T.V.3
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39
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0035971715
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For a review of the coordination of axially chiral bidentate based ligands such as MOP (2), MAP (3) and relatives, see:
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For a review of the coordination of axially chiral bidentate based ligands such as MOP (2), MAP (3) and relatives, see: McCarthy M. Guiry P.J. Tetrahedron 57 2001 3809
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(2001)
Tetrahedron
, vol.57
, pp. 3809
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McCarthy, M.1
Guiry, P.J.2
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41
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0037908201
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-1 morestable than 8b (DFT calculations were performed using the B3LYP basis set and executed through the SPARTAN interface)
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-1 morestable than 8b (DFT calculations were performed using the B3LYP basis set and executed through the SPARTAN interface)
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(1998)
Pure Appl. Chem.
, vol.70
, pp. 1035
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Prétôt, R.1
Lloyd-Jones, G.C.2
Pfaltz, A.3
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44
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84889288508
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2: submitted for publication
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2: A.V. Malkov, I. Starý, L. Gouriou, G.C. Lloyd-Jones, V. Langer, P. Spoor, V. Vinader, P. Kočovský, J. Am. Chem. Soc., submitted for publication.
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J. Am. Chem. Soc.
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Malkov, A.V.1
Starý, I.2
Gouriou, L.3
Lloyd-Jones, G.C.4
Langer, V.5
Spoor, P.6
Vinader, V.7
Kočovský, P.8
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45
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0344290112
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1H-NMR became crowded by non-alkene signals on attempting a conventional paramagnetic chiral shift reagent analysis
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1H-NMR became crowded by non-alkene signals on attempting a conventional paramagnetic chiral shift reagent analysis.
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46
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0034619611
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For an excellent overview of the technique, see
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For an excellent overview of the technique, see: M. Sarfati, P. Lesot, D. Merlet, J. Courtieu, J. Chem. Soc. Chem. Commun. (2000) 2069.
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(2000)
J. Chem. Soc. Chem. Commun.
, pp. 2069
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Sarfati, M.1
Lesot, P.2
Merlet, D.3
Courtieu, J.4
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47
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0037438418
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For a recent application of this technique to the study mechanistic issues see
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For a recent application of this technique to the study mechanistic issues see: O'Hagan D. Goss R.J.M. Meddour A. Courtieu J. J. Am. Chem. Soc. 125 2003 379
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(2003)
J. Am. Chem. Soc.
, vol.125
, pp. 379
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O'Hagan, D.1
Goss, R.J.M.2
Meddour, A.3
Courtieu, J.4
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49
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0345584257
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g we observe in 9a (72% ee) is slightly higher than the value of 68% reported by Hayashi et al. [16]. This self consistent deviation suggests that under our conditions we experience slightly more equilibration
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g we observe in 9a (72% ee) is slightly higher than the value of 68% reported by Hayashi et al. [16]. This self consistent deviation suggests that under our conditions we experience slightly more equilibration.
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50
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0345152406
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g values can be used directly calculate matched and mismatched enantioselectivities without need for regioisomeric weighting
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g values can be used directly calculate matched and mismatched enantioselectivities without need for regioisomeric weighting.
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51
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0345152407
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Unlike MAP ( 3), it seems that with MOP ( 2), a bidentate P,C-coordination may be especially favoured with small allyl units such as π-allyl or π-cycloalkenyl
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Unlike MAP ( 3), it seems that with MOP ( 2), a bidentate P,C-coordination may be especially favoured with small allyl units such as π-allyl or π-cycloalkenyl.
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53
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0344722053
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N2-type displacement of the allyl unit, thereby facilitating diastereofacial exchange, is ruled out by the stereospecificity observed in the reactions
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N2-type displacement of the allyl unit, thereby facilitating diastereofacial exchange, is ruled out by the stereospecificity observed in the reactions.
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54
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0344290108
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3-C) losingx their favourable trans relationships
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3-C) losingx their favourable trans relationships.
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55
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0345584256
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The memory effect and stereospecific nature of the Pd-catalysed reaction allow one to deduce which of the two intermediates is attacked preferentially since nucleophilic attack trans to the phosphine in 11′ gives rise to the observed major enantiomer of product ((R)- 9a). Crucial to this analysis is that the analogous complexes where the Ph ring is in the anti position (as opposed to the syn position in 11 and 11′) are not involved. Acyclic allyl complexes with solely anti-located substituent are rare. Support for this comes from the geometry of the isolated acetate complex ( 12/ 13) where Ph is in the syn position in the major regioisomer-see Ref. [16] and the lack of cis isomers of 8a evident in the product mixtures
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The memory effect and stereospecific nature of the Pd-catalysed reaction allow one to deduce which of the two intermediates is attacked preferentially since nucleophilic attack trans to the phosphine in 11′ gives rise to the observed major enantiomer of product ((R)- 9a). Crucial to this analysis is that the analogous complexes where the Ph ring is in the anti position (as opposed to the syn position in 11 and 11′) are not involved. Acyclic allyl complexes with solely anti-located substituent are rare. Support for this comes from the geometry of the isolated acetate complex ( 12/ 13) where Ph is in the syn position in the major regioisomer-see Ref. [16] and the lack of cis isomers of 8a evident in the product mixtures.
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56
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0344290110
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It is noted that the opposite argument that the more strained and less favoured regioisomer ( 10/ 10′) would be attacked preferentially under equilibrium conditions has to be invoked when the regiochemical outcome is considered. Of course, the two allyl termini are not equivalent and thus further factors must also be considered, including: (i) a greater steric interaction between nucleophile and allyl group is expected on attack of 11/ 11′ adjacent to the Ph ring; and (ii) the products are not degenerate and 8a is thermodynamically more favoured since the alkene unit is disubstituted and conjugated with the Ph ring
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It is noted that the opposite argument that the more strained and less favoured regioisomer ( 10/ 10′) would be attacked preferentially under equilibrium conditions has to be invoked when the regiochemical outcome is considered. Of course, the two allyl termini are not equivalent and thus further factors must also be considered, including: (i) a greater steric interaction between nucleophile and allyl group is expected on attack of 11/ 11′ adjacent to the Ph ring; and (ii) the products are not degenerate and 8a is thermodynamically more favoured since the alkene unit is disubstituted and conjugated with the Ph ring.
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