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ACS Catalysis
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3. CONCLUSIONS
E.; Goudriaan, P. E.; Swennenhuis, B. H. G.; Kamer, P. C. J.; van Leeuwen,
P. W. N. M.; Lutz, M.; Spek, S. L. Organometallics 2010, 29, 1210ꢀ1221.
(8) Börner, A.; Franke, R. Hydroformylation. Fundamentals, Processes
and Applications in Organic Synthesis, WileyꢀVCH: Weinheim, Germany,
2016; Vol. 1, 86ꢀ91.
(9) van der Vlugt, J. I.; Hewat, A. C.; Neto, S.; Sablong, R.; Mills, A.
M.; Lutz, M.; Spek, A. L.; Müller, C.; Vogt, D. Adv. Synth. Catal. 2004, 346,
993ꢀ1003.
(10) Goertz, W.; Kamer, P. C. J.; van Leeuwen, P. W. N. M.; Vogt, D.
Chem. Eur. J. 2001, 7, 1614ꢀ1618.
(11) van der Vlugt, I. I.; Paulusse, J. M. J.; Zijp, E. J.; Tijmensen, J. A.;
Mills, A. M.; Spek, A. L.; Claver, C.; Vogt, D. Eur. J. Inorg. Chem. 2004,
4193ꢀ4201.
In conclusion, we have discovered an easy and versatile access to enanꢀ
tiomerically pure Pꢀchirogenic Xantphos ligands and related diarylethꢀ
er diphosphines. By application of the new protocol more than 35 Pꢀ
chirogenic ligands were prepared in a convenient and efficient manner,
which is the precondition for their application in a broad range of
asymmetric transformations. The stereochemical integrity of the chiꢀ
rogenic centers over a period of two years was proved. By commonly
applied storage under argon in a refrigerator no racemization takes
place. In a first evaluation concerned to the asymmetric hydrogenation
of isophorone using corresponding rhodium complexes with some of
the ligands high conversion, almost perfect chemoselectivity and enanꢀ
tioselectivities by up to 96% were achieved.
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(12)(a) Chikkali, S. H.; Bellini, R.; BerthonꢀGelloz, G.; van der Vlugt,
J. I.; de Bruin, B.; Reek, J. N. H. Chem. Commun. 2010, 46, 1244ꢀ1246; (b)
Chikkali, S. H.; Bellini, R.; de Bruin, B.; van der Vlugt, J. I.; Reek, J. N. H. J.
Am. Chem. Soc. 2012, 134, 6607ꢀ6616.
AUTHOR INFORMATION
Corresponding Authors
(13)(a) Dierkes, P.; Ramdeehul, S.; Barloy, L.; De Cian, A.; Fischer, J.;
Kamer, P. C. J.; van Leeuwen, P. W. N. M.; Osborn, J. A.; Angew. Chem. Int.
Ed. 1998, 37, 3116ꢀ3118; (b) Ramdeehul, S.; Dierkes, P.; Aguado, R.;
Kamer, P. C. J.; van Leeuwen, P. W. N. M.; Osborn, J. A. Angew. Chem. Int.
Ed. 1998, 37, 3118ꢀ3121; (c) Malaisé, G.; Barloy, L.; Osborn, J. A.;
Kyritsakas, N. Comptes Rendues Chimie 2002, 5, 289ꢀ296; (d) Malaisé, G.;
Ramdeehul, S.; Osborn, J. A.; Barloy, L.; Kyritsakas, N.; Graff, R. Eur. J.
Inorg. Chem. 2004, 3987ꢀ4001; (e) See also: Brunker, T. J.; Blank, N. F.;
Moncarz, J. R.; Scriban, C.; Anderson, B. J.; Glueck, D. S.; Zakharov, L. N.;
Golen, J. A.; Sommer, R. D.; Incarvito, C. D.; Rheingold, A. L.
Organometallics 2005, 24, 2730ꢀ2746.
(14) For reviews on Pꢀchirogenic phosphanes compare: (a) Pieꢀ
trusiewicz, K. M.; Zablocka, M. Chem. Rev. 1994, 94, 1375ꢀ1411; (b)
Imamoto, T. Synthesis of Pꢀstereogenic Phosphines via Enantioselective
Alkylation, In Phosphorus Ligands in Asymmetric Catalysis, Börner, A., Ed.;
WileyꢀVCH: Weinheim, Germany, 2008; Vol. 3, pp 1201ꢀ1210; (c) Darcel,
C.; Uziel, J.; Jugé, S. Synthesis of Pꢀstereogenic phosphorus compounds
based on chiral amino alcohols as chiral auxiliary, In Phosphorus Ligands in
Asymmetric Catalysis, Börner, A., Ed.; WileyꢀVCH: Weinheim, Germany,
2008; Vol. 3, pp 1211ꢀ1233; (d) Grabulosa, A. P-Stereogenic Ligands in
Enantioselective Catalysis, RSC Publishing, Cambridge, 2011; (e) Koꢀ
lodiazhnyi, O. I. Asymmetric Synthesis of PꢀChirogenic Phosphorus Comꢀ
pounds, In Asymmetric Synthesis in Organophosphorus Chemistry: Synthetic
Methods, Catalysis and Applications, WileyꢀVCH: Weinheim, Germany,
2016; pp 35ꢀ100; (f) Dutarte, M.; Bayardon, J.; Jugé, S. Chem. Soc. Rev.
2016, 45, 5771ꢀ5794.
ASSOCIATED CONTENT
Supporting Information
Preparation procedures, NMR spectra of hydrolysis experiments,
hydroformylation details, Xꢀray crystallographic data, DFT calculation
results. This material is available free of charge via the Internet at
ACKNOWLEDGMENT
Dedicated to Professor Sylvain Jugé. We are grateful to Mrs. G. Wenzel
for very skilled technical assistance. Dr. Ch. Fischer, Mrs. S. Buchholz
and Mrs. S. Schareina are acknowledged for careful analysis of reaction
products. We thank BASF SE for financial support of this work.
REFERENCES
(1) Phosphorus(III) Ligands in Homogeneous Catalysis; Kamer, P. C.,
van Leeuwen , P. W. N. M., Eds.; Wiley: Chichester, UK, 2012.
(2) (a) Phosphorus Ligands in Asymmetric Catalysis, Börner, A., Ed.;
WileyꢀVCH: Weinheim, Germany, 2008, Vol. 1ꢀ3; (b) Lühr, S.; Holz, J.;
Börner, A. ChemCatChem 2011, 3, 1708ꢀ1730.
(3) Pearson, R. G. J. Am. Chem. Soc. 1963, 85, 3533ꢀ3539.
(4) (a) Tolman, C. A. Chem. Rev. 1977, 77, 313ꢀ348; (b) Allman, T.;
Goel, R. G. Can. J. Chem. 1982, 60, 716.
(5)(a) Casey, C. P.; Whiteker, G. T. Israel J. Chem. 1990, 30, 299ꢀ304;
(b) Goertz, Kamer, W.; P. C. J.; van Leeuwen, P. W. N. M.; Vogt, D. J.
Chem. Soc. Chem. Commun. 1997, 1521ꢀ1522; (c) Dierkes, P.; van
Leeuwen, P. W. N. M. Dalton Trans. 1999, 1519ꢀ1529; (d) Achord, P. D.;
Kiprof, P.; Barker, B. THEOCHEM 2008, 849, 103ꢀ111; (e) Birkholz, M.ꢀ
N.; Freixa, Z.; van Leeuwen, P. W. N. M. Chem. Soc. Rev. 2009, 38, 1099ꢀ
1118.
(15) Hamada, Y.; Matsuura, F.; Oku, M.; Hatano, K.; Shioiri, T. Te-
trahedron Lett. 1997, 38, 8961ꢀ8964.
(16)(a) Jugé, S.; Genêt J.ꢀP. (to Societe Nationale Elf Aquitaine), Fr.
Patent 8908763 (1989); Chem. Abstr. 1991, 115, 136399; (b) Kaloun, E.
B.; Merdès, R.; Genêt, J. P.; Uziel, J.; Jugé, S. J. Organomet. Chem. 1997,
529, 455ꢀ463; (c) Bayardon, J.; Jugé, S., Pꢀchiral Ligands, In Phospho-
rus(III) Ligands in Homogeneous Catalysis, Kamer, P. C. J.; van Leeuwen, P.
W. N. M., Eds.; Wiley: Chichester, UK, 2012; pp 355ꢀ389; (d) Jugé, S.
Phosphorus Sulfur Silicon Relat. Elem. 2015, 190, 600ꢀ611.
(17) For some applications of Jugé’s method for the synthesis of chiral
ligands compare: (a) Stoop, R. M.; Mezzetti, A.; Spindler, F. Organometal-
lics 1998, 17, 668ꢀ675; (b) Nettekoven, U.; Kamer, P. C. J.; Widhalm, M.;
van Leeuven, P. W. N. M. Organometallics 2000, 19, 4596ꢀ4607; (c)
Nettekoven, U.; Widhalm, M.; Kalchhauser, H.; Kamer, P. C. J.; van Leeuꢀ
wen, P. W. N. M.; Lutz, M.; Spek, A. L. J. Org. Chem. 2001, 66, 759ꢀ770;
(d) Maienza, F.; Spindler, F.; Thommen, M.; Pugin, B.; Malan, C.; Mezzetꢀ
ti, A. J. Org. Chem. 2002, 67, 5239ꢀ5249; (e) Colby, E. A.; Jamison, T. F. J.
Org. Chem. 2003, 68, 156ꢀ166; (f) Bayardon, J.; Maronnat, M.; Langlois,
A.; Rousselin, Y.; Harvey, P. D.; Jugé, S. Organometallics 2015, 34, 4340ꢀ
4358.
(6)(a) Yoon, T. P. Jacobsen, E. N. Science 2003, 299, 1691ꢀ1693; (b)
Pfaltz, A.; Drury III, W. J. PNAS 2004, 101, 5723ꢀ5726.
(7)(a) Kamer, P. C. J.; Kranenburg, M.; van Leeuwen, P. W. N. M.
Book of Abstracts, XVIth International Conference Organometallic Chemꢀ
istry, University of Sussex (10ꢀ15 July 1994), UK; The Royal Society of
Chemistry ꢀ Dalton Division, abstract no. OC 18; (b) Kamer, P. C. J.; van
Leeuwen, P. W. N. M.; de Vries, J. G. Belgium Pat. 9400470, 1994 (to DSM
N. V.), WO 9530680 (1995); (c) van der Veen, L. A.; Keeven, P. H.;
Schoemaker, G. C.; Reek, J. N. H.; Kamer, P. C. J.; van Leeuwen, P. W. N.
M.; Lutz, M.; Spek, A. L. Organometallics 2000, 19, 872ꢀ883; (d) Zuidema,
(18)(a) Nishimura, S. Handbook of heterogeneous catalytic hydrogena-
tion for organic synthesis, Wiley: New York, USA, 2001; pp 198ꢀ199; (b)
Ohkuma, T.; Noyori, T. In Handbook of homogeneous hydrogenation, de
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