A new C2-symmetric chiral diphosphine ligand: Palladium-catalyzed enantioselective allylic alkylation of cycloalkenyl substrate

Tetrahedron Asymmetry

Volumn 10, Issue 6, 1999, Pages 1025-1028

  Saitoh, Akihito ^a   Misawa, Mie ^a   Morimoto, Toshiaki ^a  

^a UNIVERSITY OF SHIZUOKA   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENYL GROUP; BUTANE; DIPHOSPHIRANE DERIVATIVE; LIGAND; PALLADIUM; VALINE;

ALKYLATION; ARTICLE; CATALYSIS; CHIRALITY; ENANTIOMER; PRIORITY JOURNAL; STEREOCHEMISTRY;

EID: 0033605614     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(99)00100-7     Document Type: Article

References (22)

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3. (a) Frost, C. G.; Howarth, J.; Williams, J. M. J. Tetrahedron: Asymmetry 1992, 3, 1089.
4. (b) Hayashi, T. In Catalytic Asymmetric Synthesis; Ojima, I., Ed. VCH: New York, 1993; Vol. 1, p. 325.
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7. (b) Saitoh, A.; Achiwa, K.; Morimoto, T. Tetrahedron: Asymmetry 1998, 9, 741.
8. 3a in which the drastic improvement of catalytic performance by electronic tuning for the ligands was demonstrated in palladium-catalyzed asymmetric allylations. Saitoh, A.; Misawa, M.; Morimoto, T. Synlett, in press.
9. (a) Trost, B. M.; Bunt, R. C. J. Am. Chem. Soc. 1994, 116, 4089.
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11. (c) Kudis, S.; Helmchen, G. Angew. Chem., Int. Ed. Engl. 1998, 37, 3047.
12. (d) Dierkes, P.; Ramdeehul, S.; Barloy, L.; Cian, A. D.; Fischer, J.; Kamer, P. C. J.; van Leeuwen, P. W. N. M.; Osborn, J. A. Angew. Chem., Int. Ed. Engl. 1998, 37, 3116.
13. Asymmetric allylations of cycloalkenyl substrates by phosphanyldihydrooxazoles, see: (a) Sennhenn, P.; Gabler, B.; Helmchen, G. Tetrahedron Lett. 1994, 35, 8595. For other P-N hybrid ligands, see:
14. (b) Brown, J. M.; Hulmes, D. I.; Guiry, P. Tetrahedron 1994, 50, 4493.
15. (c) Bourghida, M.; Widhalm, M. Tetrahedron: Asymmetry 1998, 9, 1073.
16. Whitesell, J. K. Chem. Rev. 1989, 89, 1581.
17. -1 (NH).
18. 3) δ: 1.31-1.81 (m, 4H), 1.96-2.06 (m, 2H), 2.86-2.95 (m, 1H), 3.29 (d, 1H, J=9.2 Hz), 3.74 (s, 3H), 3.75 (s, 3H), 5.52 (dd, 1H, J=2.3, 10.2 Hz), 5.74-5.82 (m, 1H).
19. 6a
20. P,P=34.8 Hz).
21. 13 as a representative diphosphine ligand, (S)-6 was produced in 34% ee under the same condition as that of entry 1. The predominant 5-selectivity was speculated upon by correlating the rotational concept with the M-chirality as depicted in Scheme 3. According to the absolute configuration of the products, a similar path may be considered in the present reactions using 1. Studies regarding the correlation of enantioselectivity with the P/M chirality are in progress. (matrix presented) Gray circles : Sterically hindered area assignable to pseudo-equatorial phenyl groups Scheme 3.
22. Sakuraba, S.; Morimoto, T.; Achiwa, K. Tetrahedron: Asymmetry 1991, 2, 597.