Angewandte
Chemie
flate products. See the Supporting Information for complete data for
all novel compounds.
(SEMI-ESPHOS; 36, 16% ee) were more encouraging although
À
MeO MOP (33, 55% ee) performed best. The use of
À
[Pd2(dba)3]/MeO MOP
(dba = trans,trans-dibenzylideneace-
tone) and CsF, dioxane conditions resulted in 30% yield and
51% ee.
Received: August 13, 2003
Revised: October 23, 2003 [Z52648]
[14] S. Breeden, D. J. Cole-Hamilton, D. F. Foster, G. J. Schwarz, M.
Wills, Angew. Chem. 2000, 112, 4272 – 4274; Angew. Chem. Int.
Ed. 2000, 39, 4106 – 4108.
[15] The absolute configuration of compound 5 was established by X-
ray diffraction analysis of the recrystallized material (97% ee).
The absolute configurations of the remaining adducts are
assigned by analogy.
[16] For reviews detailing the enantioselective construction of
quaternary centers, see: a) J. Christoffers, A. Mann, Angew.
Chem. 2001, 113, 4725 – 4732; Angew. Chem. Int. Ed. 2001, 40,
4587 – 4591; b) E. J. Corey, A. Guzman-Perez, Angew. Chem.
1998, 110, 402 – 415; Angew. Chem. Int. Ed. 1998, 37, 388 – 401;
c) K. Fuji, Chem. Rev. 1993, 93, 2037 – 2066.
Keywords: asymmetric catalysis · cross-coupling ·
enantioselectivity · palladium
.
[1] For reviews of enantioselective palladium-catalyzed coupling
reactions, see: a) T. Hayashi in Comprehensive Asymmetric
Catalysis, Vol. 2 (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto),
Springer, Berlin, 1999, pp. 887 – 907; b) M. Ogasawara, T. Hay-
ashi in Catalytic Asymmetric Synthesis, 2nd ed. (Ed.: I. Ojima),
Wiley, New York, 2000, pp. 651 – 674; c) C. G. Frost in Rodd's
Chemistry of Carbon Compounds, Vol. 5, 2nd ed. (Ed.: M.
Sainsbury), Elsevier, Amsterdam, 2001, pp. 315 – 350.
[2] For recent reviews of enantioselective Heck reactions, see: a) M.
Shibasaki, E. M. Vogl in Comprehensive Asymmetric Catalysis,
Vol. 1 (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer,
Berlin, 1999, pp. 457 – 487; b) M. Shibasaki, E. M. Vogl, J.
Organomet. Chem. 1999, 576, 1 – 15; c) O. Loiseleur, M. Hayashi,
M. Keenan, N. Schmees, A. Pfaltz, J. Organomet. Chem. 1999,
576, 16 – 22; d) Y. Donde, L. E. Overman in Catalytic Asymmet-
ric Synthesis, 2nd ed. (Ed.: I. Ojima), Wiley, New York, 2000,
pp. 675 – 697.
[17] M. C. Willis, C. K. Claverie, M. F. Mahon, Chem. Commun.
2002, 832 – 833.
[3] J. Yin, S. L. Buchwald, J. Am. Chem. Soc. 2000, 122, 12051 –
12052.
[4] A. N. Cammidge, K. V. L. CrØpy, Chem. Commun. 2000, 1723 –
1724.
[5] For the application of an antropo-enantioselective Suzuki
reaction to the synthesis of the analogues of rhazinilam, see:
A. Herrbach, A. Marinetti, O. Baudoin, D. GuØnard, F. GuØritte,
J. Org. Chem. 2003, 68, 4897 – 4905.
[6] a) T. Hayashi, K. Hayashizaki, T. Kiyoi, Y. Ito, J. Am. Chem. Soc.
1988, 110, 8153 – 8156; b) T. Hayashi, S. Niizuma, T. Kamikawa,
N. Suzuki, Y. Uozumi, J. Am. Chem. Soc. 1995, 117, 9101 – 9102;
c) T. Kamikawa, T. Hayashi, Tetrahedron 1999, 55, 3455 – 3466.
[7] a) M. Uemura, H. Nishimura, T. Hayashi, J. Organomet. Chem.
1994, 473, 129 – 137. For a palladium-catalyzed carbonylation
route to planar chiral systems, see: b) B. Gotov, H.-G. Schmalz,
Org. Lett. 2001, 3, 1753 – 1756.
[8] For a desymmetrization-based enantioselective intramolecular
Suzuki coupling that delivers products with selectivities up to
31% ee, see: S. Y. Cho, M. Shibasaki, Tetrahedron: Asymmetry
1998, 9, 3751 – 3754.
[9] For a review of enantioselective desymmetrization, see: M. C.
Willis, J. Chem. Soc. Perkin Trans. 1 1999, 1765 – 1784.
[10] For reviews of Suzuki reactions, see: a) N. Miyaura, A. Suzuki,
Chem. Rev. 1995, 95, 2457 – 2483; b) A. Suzuki, J. Organomet.
Chem. 1999, 576, 147 – 168.
[11] For the synthesis of 1a and its use in achiral Suzuki couplings,
see: M. C. Willis, C. K. Claverie, Tetrahedron Lett. 2001, 42,
5105 – 5107.
[12] For the use of substrates related to 1a in enantioselective
intramolecular Heck reactions, see: S. Bräse, Synlett 1999, 1654 –
1656.
[13] Initial catalyst evaluation was conducted using a KOH–THF
combination at room temperature; bidentate ligands such as 2,2’-
bis(diphenylphosphanyl)-1,1’-binaphthyl (BINAP), O-isopropy-
lidene-2,3-dihydroxy-1,4-bis(diphenylphosphanyl)butane
(DIOP), and 2,3-bis(diphenylphosphanyl)butane (CHIRA-
PHOS) produced inactive catalysts. 4,12-Bis(diphenylphos-
phanyl)-[2,2]paracyclophane (PHANEPHOS; 36, 12% ee), neo-
menthyldiphenylphosphane (29, 6% ee), and 1-(2-methoxy-
phenyl)-2-phenylhexahydropyrrolo[1,2-c][1,3,2]diazaphosphole[14]
Angew. Chem. Int. Ed. 2004, 43, 1249 –1251
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