ORGANIC
LETTERS
2
006
Vol. 8, No. 7
479-1481
Enantioselective Rhodium-Catalyzed
Addition of Arylboronic Acids to
Aldehydes Using Chiral Spiro
Monophosphite Ligands
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Hai-Feng Duan, Jian-Hua Xie, Wen-Jian Shi, Qi Zhang, and Qi-Lin Zhou*
State Key Laboratory and Institute of Elemento-organic Chemistry, Nankai UniVersity,
Tianjin 300071, China
Received February 10, 2006
ABSTRACT
Highly efficient rhodium-catalyzed asymmetric addition of arylboronic acids to aldehydes has been realized by using chiral spiro monophosphite
ligands, affording diarylmethanols in excellent yields and good enantiomeric excesses.
Catalytic asymmetric carbon-carbon bond formation was
one of the most studied subjects in the past few decades. In
these studies, the enantioselective addition of aryl organo-
metallic reagents to aldehydes remains to be an extremely
attractive topic because the products, secondary aryl alcohols,
are important intermediates for the synthesis of biologically
naphthaldehyde by using the (S)-MeO-MOP ligand giving
3a
naphthylphenylmethanol in 78% yield and 41% ee. To the
best of our knowledge, this result is so far the highest
enantioselectivity for Rh-catalyzed addition of aryl organo-
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metallic reagents to aldehydes. Thus, the search for efficient
chiral ligands to achieve high enantioselectivity in this very
useful reaction is the goal of many efforts.
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and pharmaceutically active compounds. Recently, great
progress has been achieved in the amino alcohol mediated
enantioselective addition of pre-prepared or in situ generated
arylzinc reagents to aldehydes. However, the examples for
Recently, we have developed new types of monodentate
chiral phosphoramidites and phosphonites based on 1,1′-
spiro-biindane-7.7′-diol and demonstrated that they were
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the transition-metal-catalyzed asymmetric additions of aryl
organometallic reagents to aldehydes are quite limited. In
3
(3) For asymmetric Rh-catalyzed addition of organometallic reagents to
aldehydes, see: (a) Sakai, M.; Ueda, M.; Miyaura, N. Angew. Chem., Int.
Ed. 1998, 37, 3279. (b) Moreau, C.; Hague, C.; Weller, A. S.; Frost, C. G.
Tetrahedron Lett. 2001, 42, 6957. (c) Fuchen, T.; Rudolph, J.; Bolm, C.
Synthesis 2005, 429. For nonasymmetric Rh-catalyzed addition of aryl
organometallic reagents to aldehydes, see: (a) Oi, S.; Moro, M.; Inoue, Y.
Chem. Commun. 1997, 1621. (b) Ueda, M.; Miyaura, N. J. Org. Chem.
2000, 65, 4450. (c) Li, C.-H.; Meng, Y. J. Am. Chem. Soc. 2000, 122,
9538. (d) Huang, T.; Meng, Y.; Venkatraman, S.; Wang, D.; Li, C.-H. J.
Am. Chem. Soc. 2001, 123, 7451. (e) F u¨ rstner, A.; Krause, H. AdV. Synth.
Catal. 2001, 343, 343. (f) Oi, S.; Moro, M.; Inoue, Y. Organometallics
2001, 20, 1036. (g) Fujii, T.; Koike, T.; Mori, A.; Osakada, K. Synlett 2002,
298. (h) Oi, S.; Moro, M.; Fukuhara, H.; Kawanishi, T.; Inoue, Y.
Tetrahedron 2003, 59, 4351.
1998, Miyaura and co-workers initially reported the enan-
tioselective Rh-catalyzed addition of phenylboronic acid to
(1) (a) Casy, A. F.; Drake, A. F.; Ganellin, C. R.; Mercer, A. D.; Upton,
C. Chirality 1992, 4, 356. (b) Spencer, C. M.; Foulds, D.; Peter, D. H.
Drugs 1993, 46, 1055. (c) Botta, M.; Summa, V.; Corelli, F.; Pietro, G. D.;
Lombardi, P. Tetrahedron: Asymmetry 1996, 7, 1263.
(
2) (a) Dosa, P. I.; Ruble, J. C.; Fu, G. C. J. Org. Chem. 1997, 62, 444.
(
b) Huang, W.-S.; Hu, Q.-S.; Pu, L. J. Org. Chem. 1999, 64, 7940. (c)
Bolm, C.; Hermanns, N.; Hildebrand, J. P.; Mu n˜ iz, K. Angew. Chem., Int.
Ed. 2000, 39, 3465. (d) Bolm, C.; Rudolph, J. J. Am. Chem. Soc. 2002,
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24, 14850. (e) Montserrat, F.; Xavier, V.; Lluis, S.; Miquel, A. P.; Antoni,
(4) For enantioselective Rh-catalyzed conjugate addition of arylboronic
acids to enones and other compounds, see: (a) Hayashi, T. Synlett 2001,
879. (b) Hayashi, T.; Yamasaki, K. Chem. ReV. 2003, 103, 2829.
R. J. Org. Chem. 2004, 69, 2532. (f) Braga, A. L.; L u¨ dtke, D. S.; Vargas,
F.; Paix a˜ o, M. W. A. Chem. Commun. 2005, 19, 2512.
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0.1021/ol060360c CCC: $33.50
© 2006 American Chemical Society
Published on Web 03/09/2006