Advanced Synthesis & Catalysis
10.1002/adsc.201701591
temperature under argon. All volatiles were evaporated [5] For studies of N,P derived iridium-dihydride
under reduced pressure (700 mbar 10 mbar, 40 °C),
whereby most of the COD was removed. The residue was
purified by column chromatography (silica gel d × h: 2 cm
complexes, see: a) C. Mazet, S. P. Smidt, M. Meuwly,
A. Pfaltz, J. Am. Chem. Soc. 2004, 126, 14176-14181;
b) S. Gruber, M. Neuburger, A. Pfaltz,
×
Et
5 cm) by first eluting the hydrogenated product with
O/pentane (1/1) (~100 mL), followed by eluting the
Cl (~40 mL). The separate fractions
were concentrated in a rotary evaporator (700 mbar 10
Organometallics 2013, 32, 4702-4711; c) S. Gruber, A.
Pfaltz, Angew. Chem., Int. Ed. 2014, 53, 1896-1900; d)
Y. Liu, I. D. Gridnev, W. Zhang, Angew. Chem., Int.
Ed. 2014, 53, 1901-1905; e) S. Gruber,
2
catalyst with CH
2
2
-
1
mbar, 40 °C) and dried under high-vacuum (~10 mbar, 30
min, rt) to afford the hydrogenated product free of COD in
Organometallics 2016, 35, 699-705; f) M.-L. Li, S.
Yang, X.-C. Su, H.-L. Wu, L.-L. Yang, S.-F. Zhu, Q.-L.
Zhou, J. Am. Chem. Soc. 2017, 139, 541-547
[6] S. P. Smidt, A. Pfaltz, E. Martínez-Viviente, P. S.
Pregosin, A. Albinati, Organometallics 2003, 22, 1000-
1009.
9
9% yield (381 mg) and the recovered catalyst 6 in 60%
yield (18.1 mg), respectively.
For the hydrogenation of (E)-1,2-diphenyl-1-propene (11)
with catalysts 9 and 10 and recovery of those, the same [7] S. P. Smidt, N. Zimmermann, M. Studer, A. Pfaltz,
procedure as described for catalyst 6 was applied, using
Chem.– Eur. J. 2004, 10, 4685-4693.
.93 mmol and 1.45 mmol, respectively, of (E)-1,2- [8] Gridnev and co-workers have shown by low-
1
diphenyl-1-propene (11).
temperature NMR studies that N,P derived hydride-
bridged dinuclear iridium pentahydride complexes
equilibrate in solution via a hydride-bridged dinuclear
iridium tetrahydride complex to mononuclear dihydride
iridium(III) complexes of the forumula
The analytical data of the recovered catalyst 5, 6,[12] and
[
12]
[
13]
9
and the hydrogenation products propane-1,2-
[
14]
diyldibenzene
and
(6R,10R)-6,10,14-
[
15]
trimethylpentadecan-2-one are consistent with literature
values.
2 F
[Ir(H) (BiphPHOX)]BAr .; see ref [5d]
[9] In the hydrogenation of (E)-1,2-diphenyl-1-propene
with 0.1 mol% of catalyst 1, similar conversion but
lower enantioselectivity was observed using 0.2 mol%
Acknowledgements
[
H(OEt
to 78% while conversion reached 10% and 12%,
respectively (50 bar H , RT, 2 h).
2 2 F
) ]BAr as additive. The ee dropped from 92%
We are thankful to Achim Link for synthetic contributions.
Support by the Swiss National Science Foundation is gratefully
acknowledged
2
[10] a) S. Bell, B. Wüstenberg, S. Kaiser, F. Menges, T.
Netscher, A. Pfaltz, Science 2006, 311, 642-644; b) A.
Wang, B. Wüstenberg, A. Pfaltz, Angew. Chem., Int.
Ed. 2008, 47, 2298-2300.
References
[
11] We have recently reported two structures with the
formula [IrH(C,N)(-H)] (BAr with a hydride shift
trans to an empty coordination site appearing at = -
6.85 and -34.45 ppm, respectively; See ref. [5b]. See
also: a) H. E. Selnau, J. S. Merola, Organometallics
993, 12, 3800-3801; b) N. M. Scott, V. Pons, E. D.
2
F 2
)
[
1] a) X. Cui, K. Burgess, Chem. Rev. 2005, 105, 3272-
3
2
296; b) S. J. Roseblade, A. Pfaltz, Acc. Chem. Res.
007, 40, 1402-1411; c) T. L. Church, P. G. Andersson,
3
Coord. Chem. Rev. 2008, 252, 513-531; d) D.
Woodmansee, A. Pfaltz, Top. Organomet. Chem. 2011,
1
Stevens, D. M. Heinekey, S. P. Nolan, Angew. Chem.
Int. Ed. 2005, 44, 2512-2515; c) M. R. Castillo, M.
Mart_n, J. M. Fraile, J. A. Mayoral, E. Sola, Angew.
Chem. Int. Ed. 2011, 50, 3240 – 3243. For a structure
with a hydride ligand positioned trans to a
3
4, 31-76; e) D. H. Woodmansee, A. Pfaltz, Chem.
Commun. 2011, 47, 7912-7916; f) A. Cadu, P. G.
Andersson, J. Organomet. Chem. 2012, 714, 3-11; g) J.
J. Verendel, O. Pàmies, M. Diéguez, P. G. Andersson,
Chem. Rev. 2014, 114, 2130-2169; h) O. Pàmies, M.
Magre, M. Diéguez, Chem. Rec. 2016, 16, 1578-1590;
i) C. Margarita, P. G. Andersson, J. Am. Chem. Soc.
dichloromethane molecule with the formula
[
IrH(CH
12] S. Kaiser, S. P. Smidt, A. Pfaltz, Angew. Chem., Int. Ed.
006, 45, 5194-5197
2
Cl
2
)(N,P)(-H)]
2 F 2
(BAr ) ; See ref. [5b].
[
[
[
[
2
017, 139, 1346-1356.
2
[
[
2] a) G. Shang, W. Li, X. Zhang, in Catalytic Asymmetric
13] V. Semeniuchenko, V. Khilya, U. Groth, Z. Naturforsch.
B, 2009, 64, 1147-1158.
14] C. E. Hartmann, V. Jurcik, O. Songis, C. S. J. Cazin,
Chem. Commun. 2013, 49, 1005-1007.
Synthesis (Ed.: I. Ojima), John Wiley & Sons, Inc.,
2
010, pp. 343-436; b) D. J. Ager, A. H. M. de Vries, J.
G. de Vries, Chem. Soc. Rev. 2012, 41, 3340-3380.
3] a) D. J. Cole-Hamilton, Science 2003, 299, 1702-1706;
b) D. E. De Vos, I. F. J. Vankelecom P. A. Jacobs
Chiral Catalyst Immobilization and Recycling, Wiley-
VCH, Weinheim, 2007; c) A. F. Trindade, P. M. P.
Gois, C. A. M. Afonso, Chem. Rev. 2009, 109, 418-
15] T. Suga, S. Ohta, A. Nakai, K. Munesada, J. Org. Chem.
1
989, 54, 3390-3393.
5
14; d) G. Chauhan, K. K. Pant, K. D. P. Nigam, Ind.
Eng. Chem. Res. 2013, 52, 16724-16736.
[
4] J. Bayardon, J. Holz, B. Schäffner, V. Andrushko, S.
Verevkin, A. Preetz, A. Börner, Angew. Chem., Int. Ed.
2
007, 46, 5971-5974.
5
This article is protected by copyright. All rights reserved.