Full Paper
[8]
[9]
K. Tanaka, K. Kukita, T. Ichibakase, S. Kotanib, M. Nakajima, Chem. Com-
mun. 2011, 47, 5614–5616.
J = 6.4 Hz, 1 H), 2.04 (s, 3 H), 1.57–1.44 (m, 4 H), 1.38–1.18 (m, 14
H), 0.94–0.82 (m, 6 H) ppm. 13C NMR (100.6 MHz, CDCl3): δ = 171.0,
74.4, 34.1, 33.8, 31.8, 29.5, 29.2, 27.5, 25.3, 22.6, 22.6, 21.3, 14.1,
14.0 ppm. HRMS (+ESI): calcd. for C14H28O2Na [M + Na]+ 251.1987,
found 251.1975. ee determination by chiral GC analysis, CP Chirasil-
DEX CB column, T = 115 °C, P = 6 psi, retention time: tr(S) = 51.4 min,
tr(R) = 52.2 min (major enantiomer).
For some examples of natural product syntheses with a chiral methyl
carbinol moiety, see: a) F. Cohen, L. E. Overman, J. Am. Chem. Soc. 2006,
128, 2604–2608; b) G. Sabitha, C. S. Reddy, J. S. Yadav, Tetrahedron Lett.
2006, 47, 4513–4516; c) M. S. Scott, C. A. Luckhurst, D. J. Dixon, Org. Lett.
2005, 7, 5813–5816; d) G. Pattenden, D. J. Critcher, M. Remunian, Can. J.
Chem. 2004, 82, 353–365; e) G. B. Jones, M. Guzel, B. J. Chapman, Tetrahe-
dron: Asymmetry 1998, 9, 901–905; f) S. Hanessian, Total Synthesis of
Natural Products: The Chiron Approach, Pergamon, Oxford, 1983.
For some general reviews on the addition of organozinc reagents to
carbonyl compounds, see: a) C. M. Binder, B. Singaram, Org. Prep. Proced.
Int. 2011, 43, 139–208; b) D. J. Ramón, M. Yus, Chem. Rev. 2006, 106,
2126–2208; c) M. Yus, D. J. Ramón, Pure Appl. Chem. 2005, 77, 2111–
2119; d) M. Yus, D. J. Ramón, Recent Res. Dev. Org. Chem. 2002, 6, 297–
378; e) L. Pu, H.-B. Yu, Chem. Rev. 2001, 101, 757–824; f) A. Lemiere, A.
Côté, M. K. Janes, A. B. Charette, Aldrichim. Acta 2009, 42, 71–83; g) J.
Balsells, T. J. Davis, P. Carroll, P. J. Walsh, J. Am. Chem. Soc. 2002, 124,
10336–10348.
Acknowledgments
[10]
B. M. thanks the European Commission for a Marie Curie Career
Integration Grant, the Engineering and Physical Sciences Re-
search Council (EPSRC) for a First Grant and the Royal Society
for a travel grant. G. P. Howell is thanked for helpful comments
on the manuscript.
[11]
For enantioselective additions of Grignard reagents to carbonyl groups
with stoichiometric amounts of chiral ligands, see ref.[3a] and: a) H. G.
Richey, New Developments: Grignard Reagents, Wiley, Chichester, UK,
2000; b) B. J. Wakefield, Organomagnesium Methods in Organic Synthesis,
Academic Press, San Diego, CA, 1995. For enantioselective additions of
Grignard reagents with catalytic amounts of chiral ligands, see: c) A. V. R.
Madduri, S. R. Harutyunyan, A. J. Minnaard, Angew. Chem. Int. Ed. 2012,
51, 3164–3167; Angew. Chem. 2012, 124, 3218–3221; d) A. V. R. Madduri,
A. J. Minnaard, S. R. Harutyunyan, Chem. Commun. 2012, 48, 1478–1480;
e) E. Fernández-Mateos, B. Maciá, D. J. Ramón, M. Yus, Eur. J. Org. Chem.
2011, 6851–6855; f) D. Itakura, T. Harada, Synlett 2011, 2875–2879; g) Y.
Liu, C.-S. Da, S.-L. Yu, X.-G. Yin, J.-R. Wang, X.-Y. Fan, W.-P. Li, R. Wang, J.
Org. Chem. 2010, 75, 6869–6878; h) X.-Y. Fan, Y.-X. Yang, F.-F. Zhuo, S.-L.
Yu, X. Li, Q.-P. Guo, Z.-X. Du, C.-S. Da, Chem. Eur. J. 2010, 16, 7988–7991;
i) C.-S. Da, J.-R. Wang, X.-G. Yin, X.-Y. Fan, Y. Liu, S.-L. Yu, Org. Lett. 2009,
11, 5578–5581; j) Y. Muramatsu, T. Harada, Angew. Chem. Int. Ed. 2008,
47, 1088–1090; Angew. Chem. 2008, 120, 1104–1106; k) Y. Muramatsu, T.
Harada, Chem. Eur. J. 2008, 14, 10560–10563; l) A. V. R. Madduri, A. J.
Minnaard, S. R. Harutyunyan, Org. Biomol. Chem. 2012, 10, 2878–2884;
m) Z. Wu, A. V. R. Madduri, S. R. Harutyunyan, A. J. Minnaard, Eur. J. Org.
Chem. 2014, 575–582; n) E. Fernández-Mateos, B. Maciá, M. Yus, Eur. J.
Org. Chem. 2014, 6519–6526; o) H. Pellissier, Tetrahedron 2015, 71, 2487–
2524.
Keywords: Organolithium reagents · Titanium · Ar-BINMOL ·
Aldehydes · Enantioselective catalysis
[1] a) R. Noyori, in Asymmetric Catalysts in Organic Synthesis, Wiley, New
York, 1994; b) Transition Metals for Organic Synthesis, vols. I and II (Eds.:
M. Beller, C. Bolm), Wiley-VCH, Weinheim, 1998; c) Comprehensive Asym-
metric Catalysis (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer,
Berlin, 1999; d) Catalytic Asymmetric Synthesis, 2nd ed. (Ed.: I. Ojima),
Wiley-VCH, New York, 2000; e) G. Poli, G. Giambastiani, A. Heumann,
Tetrahedron 2000, 56, 5959–6150; f) E. Negishi, in: Handbook of Organo-
palladium Chemistry for Organic Synthesis, John Wiley & Sons, Inc., Ho-
boken, NJ, 2002, vol. 2, pp. 1689–1705; g) A. de Meijere, P. von Zez-
schwitz, H. Nüske, B. Stulgies, J. Organomet. Chem. 2002, 653, 129–140;
h) Transition Metals for Organic Synthesis, 2nd ed. (Eds.: M. Beller, C.
Bolm), Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2004; i) L. F.
Tietze, I. Hiriyakkanavar, H. P. Bell, Chem. Rev. 2004, 104, 3453–3516; j)
M. Schlosser in Organometallics in Synthesis, Third Manual, Wiley-VCH,
Weinheim, 2013; k) F. R. Hartley, S. Patai in Carbon–Carbon Bond Forma-
tion Using Organometallic Compounds, Wiley, New York, 1985.
[2] a) Z. Rappoport, I. Marek in The Chemistry of Organolithium Compounds,
Wiley-VCH, Weinheim, 2004; b) C. Nájera, M. Yus, Curr. Org. Chem. 2003,
7, 867–926.
[3] a) M. R. Luderer, W. F. Bailey, M. R. Luderer, J. D. Fair, R. J. Dancer, M. B.
Sommer, Tetrahedron: Asymmetry 2009, 20, 981–998; b) M. Hatano, T.
Miyamoto, K. Ishihara, Curr. Org. Chem. 2007, 11, 127–157; c) H. J. Zhu,
J. X. Jiang, J. Ren, Y. M. Yan, C. U. Pittman, Curr. Org. Synth. 2005, 2, 547–
587; d) R. Noyori, M. Kitamura, Angew. Chem. Int. Ed. Engl. 1991, 30, 49–
69; Angew. Chem. 1991, 103, 34–55; e) D. M. Hodgson in Organolithiums
in Enantioselective Chemistry, Springer, Berlin, 2003; f) G. Wu, M. Huang,
Chem. Rev. 2006, 106, 2596–2616; g) G. G. Wu, M. Huang, Top. Orga-
nomet. Chem. 2004, 6, 1–35; h) G. P. Howell, Org. Process Res. Dev. 2012,
16, 1258–1272.
[12]
[13]
B. Lecachey, C. Fressigné, H. Oulyadi, A. Harrison-Marchand, J. Maddal-
uno, Chem. Commun. 2011, 47, 9915–9917.
For the transmetallation of alkyllithium reagents to less reactive
RTi(OiPr)3, see: a) B. Weber, D. Seebach, Tetrahedron 1994, 50, 7473–7484.
For the transmetallation of aryllithium reagents to zinc reagents, see: b)
L. Salvi, J. G. Kim, P. J. Walsh, J. Am. Chem. Soc. 2009, 131, 12483–12493.
For the transmetallation of aryllithium reagents to magnesium deriva-
tives, see: c) Y. Nakagawa, Y. Muramatsu, T. Harada, Eur. J. Org. Chem.
2010, 34, 6535–6538.
a) E. Fernández-Mateos, B. Maciá, M. Yus, Eur. J. Org. Chem. 2012, 3732–
3736. For the enantioselective addition of other organometallic reagents
with Ar-BINMol ligands, see ref.[11e,11n] and: b) E. Fernández-Mateos, B.
Maciá, M. Yus, Tetrahedron: Asymmetry 2012, 23, 789–794; c) L.-S. Zheng,
K.-Z. Jiang, Y. Deng, X.-F. Bai, G. Gao, F.-L. Gu, L.-W. Xu, Eur. J. Org. Chem.
2013, 4, 748–755.
For the synthesis of Ar-BINMOLs, see: a) G. Gao, F.-L. Gu, J.-X. Jiang, K.
Jiang, C.-Q. Sheng, G.-Q. Lai, L.-W. Xu, Chem. Eur. J. 2011, 17, 2698–2703.
For other applications of Ar-BINMOLs in asymmetric catalysis, see: b) G.
Gao, X.-F. Bai, H.-M. Yang, J.-X. Jiang, G.-Q. Lai, L.-W. Xu, Eur. J. Org. Chem.
2011, 5039–5046; c) Z. Xu, L.-W. Xu, Chem. Rec. 2015, 15, 925–948.
E. Fernández-Mateos, B. Maciá, M. Yus, Adv. Synth. Catal. 2013, 355, 1249–
1254.
[14]
[4] J. Graff, E. Łastawiecka, L. Guénée, F. Leroux, A. Alexakis, Adv. Synth. Catal.
2015, 357, 2833–2839.
[5] a) T. K. Beng, R. E. Gawley, J. Am. Chem. Soc. 2010, 132, 12216–12217; b)
J. L. Bilke, S. P. Moore, P. O'Brien, J. Gilday, Org. Lett. 2009, 11, 1935–1938.
[6] a) A. Alexakis, F. Amiot, Tetrahedron: Asymmetry 2002, 13, 2117–2122; b)
S. E. Denmark, O. J.-C. Nicaise, Chem. Commun. 1996, 999–1004; c) S. E.
Denmark, N. Nakajima, O. J.-C. Nicaise, J. Am. Chem. Soc. 1994, 116,
8798–8798; d) I. Inoue, I. Mitsuru, S. Kenji, K. Koga, K. Tomioka, Tetrahe-
dron 1994, 50, 4429–4438; e) K. Tomioka, I. Inoue, I. Mitsuru, S. Kenji, K.
Koga, Tetrahedron Lett. 1991, 32, 3095–3098.
[7] a) M. Fañanás-Mastral, M. Pérez, P. H. Bos, A. Rudolph, S. R. Harutyunyan,
B. L. Feringa, Angew. Chem. Int. Ed. 2012, 51, 1922–1925; Angew. Chem.
2012, 124, 1958–1961; b) M. Pérez, M. Fañanás-Mastral, P. H. Bos, A. Ru-
dolph, S. R. Harutyunyan, B. L. Feringa, Nature Chem. 2011, 3, 377–381;
c) F. Gao, Y. Lee, K. Mandai, A. H. Hoveyda, Angew. Chem. Int. Ed. 2010,
49, 8370–8374; Angew. Chem. 2010, 122, 8548–8552; d) K. Tanaka, J. Mat-
suui, H. Suzuki, J. Chem. Soc. Perkin Trans. 1 1993, 153–157.
[15]
[16]
[17]
[18]
X. Ren, G. Li, S. Wei, H. Du, Org. Lett. 2015, 17, 990–993.
For [α]D values, see: J. Guo, J. Chen, Chem. Commun. 2015, 51, 5725–
5728. For NMR spectroscopic data, see ref.[16]
[19]
For [α]D values, see: a) F. Li, N. Wang, L. Lu, G. Zhu, J. Org. Chem. 2015,
80, 3538–3546. For NMR spectroscopic data, see: b) Q.-M. Zhu, D.-J. Shi,
C.-G. Xia, H.-M. Huang, Chem. Eur. J. 2011, 17, 7760–7763.
Eur. J. Org. Chem. 2016, 1788–1794
1793
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim