10.1002/anie.201711363
Angewandte Chemie International Edition
COMMUNICATION
[5]
[6]
3-AMIQ
=
3-aminomethylisoquinoline.
BINAP
=
2,2’-
the reactions with S/Cs of 500 and 5000.
chemoselectivity producing hydroxy esters or diols was precisely
controlled just by changing the reaction conditions. The
reactivity of the ester group was significantly dependent on the
length of the carbon-spacer between the two carbonyl moieties.
The reaction of β- and ε-keto esters under both conditions
selectively afforded the hydroxy esters. The enantioselective
and ester regio (position)-selective hydrogenation of a γ-ε-diketo
diester into the tri-hydroxy ester was also achieved.
Thus, the
bis(diphenylphosphanyl)-1,1’-binaphthyl. DIPSkewphos = 2,4-bis[(3,5-
diisopropyl)phenylphosphanyl]pentane. XylSkewphos
xylylphosphanyl)pentane.
= 2,4-bis(3,5-
a) T. Ohkuma, C. A. Sandoval, R. Srinivasan, Q. Lin, Y. Wei, K. Muñiz,
R. Noyori, J. Am. Chem. Soc. 2005, 127, 8288–8289; b) N. Arai, K.
Suzuki, S. Sugizaki, H. Sorimachi, T. Ohkuma, Angew. Chem. 2008,
120, 1794–1797; Angew. Chem. Int. Ed. 2008, 47, 1770–1773; c) K.
Tsutsumi, T. Katayama, N. Utsumi, K. Murata, N. Arai, N. Kurono, T.
Ohkuma, Org. Process Res. Dev. 2009, 13, 625–628; d) T. Ohkuma, N.
Arai, Chem. Rec. 2016, 16, 2801–2819.
[7]
[8]
For
transfer
hydrogenation
of
ketones
by
using
[RuCl2(diphosphane)(pica)], see: W. Baratta, E. Herdtweck, K. Siega, M.
Toniutti, P. Rigo, Organometallics 2005, 24, 1660–1669.
Acknowledgements
For asymmetric hydrogenation of ethyl 4-oxo-4-phenylbutanoate into
the hydroxy esters catalyzed by BINAP–Ru(II) complexes, see: a) T.
Ohkuma, M. Kitamura, R. Noyori, Tetrahedron Lett. 1990, 31, 5509–
5512 ([Ru(OCOCH3)2(binap)]–HCl, S/C = 333, 100 atm H2, 35°C, 258 h,
30% yield, 97% ee); b) E. V. Starodubtseva, O. V. Turova, M. G.
Vinogradov, L. S. Gorshkova, V. A. Ferapontov, M. I. Struchkova,
Tetrahedron 2008, 64, 11713–11717 ([RuCl3]–BINAP–HCl, S/C = 500,
60 atm H2, 60°C, 65 h, 65% yield, 91% ee).
We thank Dr. T. Katayama and Mr. N. Utsumi at Kanto Chemical
Co., Inc. for useful discussion on production of the
DIPSkewphos/3-AMIQ–Ru(II) complex.
This work was
supported by a Grant-in-Aid from the Japan Society for the
Promotion of Science (JSPS) (No. 15H03802) and a grant from
the MEXT (Japan) program "Strategic Molecular and Materials
Chemistry through Innovative Coupling Reactions" of Hokkaido
University.
[9]
a) T. Ohkuma, H. Ooka, S. Hashiguchi, T. Ikariya, R. Noyori, J. Am.
Chem. Soc. 1995, 117, 2675–2676; b) H. Doucet, T. Ohkuma, K.
Murata, T. Yokozawa, M. Kozawa, E. Katayama, A. F. England, T.
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Chem. 2001, 113, 40–75; Angew. Chem. Int. Ed. 2001, 40, 40–73.
DPEN = 1,2-diphenylethylenediamine.
Keywords: asymmetric catalysis • chemoselectivity •
hydrogenation • keto esters • ruthenium
[10] For asymmetric hydrogenation of δ- and ε-keto esters into the hydroxy
esters, see: a) B. S. Lucas, B. Fisher, L. R. McGee, S. H. Olson, J. C.
Medina, E. Cheung, J. Am. Chem. Soc. 2012, 134, 12855–12860; b) S.
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H. Senanayake, Adv. Synth. Catal. 2014, 356, 301–307; c) G.-L. Zhu,
X.-D. Zhang, L.-J. Yang, J.-H. Xie, D.-Q. Che, Q. L. Zhou, P.-C. Yan,
Y.-Q. Li, Org. Process Res. Dev. 2016, 20, 81–85.
[1]
For selected reviews, see: a) T. Ohkuma, R. Noyori in Transition Metals
for Organic Synthesis, 2nd ed., Vol. 2 (Eds.: M. Beller, C. Bolm), Wiley-
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C. J. Elsevier), Wiley-VCH, Weinheim, 2007, pp 1105–1163; c) N. Arai,
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N. Arai in Comprehensive Chirality, Vol. 5 (Eds.: E. M. Carreira, H.
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a) R. Noyori, T. Ohkuma, M. Kitamura, H. Takaya, N. Sayo, H.
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32.
[11] For
hydrogenation
of
β-aryl-β-keto
esters
with
excellent
enantioselectivity, see for example: a) Y.-G. Zhou, W. Tang, W.-B.
Wang, W. Li, X. Zhang, J. Am. Chem. Soc. 2002, 124, 4952–4953; b) A.
Hu, H. L. Ngo, W. Lin, Angew. Chem. 2004, 116, 2555–2558; Angew.
Chem. Int. Ed. 2004, 43, 2501–2504; c) T. Imamoto, M. Nishimura, A.
Koide, K. Yoshida, J. Org. Chem. 2007, 72, 7413–7416; d) X. Sun, W.
Li, G. Hou, L. Zhou, X. Zhang, Adv. Synth. Catal. 2009, 351, 2553–
2557; e) J.-H. Xie, X.-Y. Liu, X.-H. Yang, J.-B. Xie, L.-X. Wang, Q.-L.
Zhou, Angew. Chem. 2012, 124, 205–207; Angew. Chem. Int. Ed. 2012,
51, 201–203.
[2]
[3]
[4]
X.-H. Yang, J.-H. Xie, W.-P. Liu, Q.-L. Zhou, Angew. Chem. 2013, 125,
7987–7990; Angew. Chem. Int. Ed. 2013, 52, 7833–7836. For kinetic
resolution of δ-hydroxy esters by asymmetric hydrogenation, see: X.-H.
Yang, K. Wang, S.-F. Zhu, J.-H. Xie, Q.-L. Zhou, J. Am. Chem. Soc.
2014, 136, 17426–17429.
[12] For achiral hydrogenation of δ-lactones with the BINAP/DPEN–Ru(II)
catalyst, see: S. Takebayashi, S. H. Bergens, Organometallics 2009, 28,
2349–2351.
For achiral hydrogenation of α-keto esters into the α-hydroxy esters or
the 1,2-diols, see: S. Gao, W. Tang, M. Zhang, C. Wang, J. Xiao,
Synlett 2016, 27, 1748–1752.
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