DOI: 10.1002/anie.200250861. Enhancing the Enantioselectivity of Novel Homogeneous Organometallic Hydrogenation Catalysts

Enhancing the Enantioselectivity of Novel Homogeneous Organometallic Hydrogenation Catalysts

10.1002/anie.200250861

Crossref journal-article

Wiley

Angewandte Chemie International Edition (311)

Bibliography

Jones, M. D., Raja, R., Thomas, J. M., Johnson, B. F. G., Lewis, D. W., Rouzaud, J., & Harris, K. D. M. (2003). Enhancing the Enantioselectivity of Novel Homogeneous Organometallic Hydrogenation Catalysts. Angewandte Chemie International Edition, 42(36), 4326â4331. Portico.

Authors 7

Matthew D. Jones (first)
Robert Raja (additional)
John Meurig Thomas (additional)
Brian F. G. Johnson (additional)
Dewi W. Lewis (additional)
Jacques Rouzaud (additional)
Kenneth D. M. Harris (additional)

References 39 Referenced 176

{'key': 'e_1_2_3_1_2', 'volume-title': 'Homogeneous Catalysis', 'author': 'Parshall G. W.', 'year': '1992'} / Homogeneous Catalysis by Parshall G. W. (1992)
{'key': 'e_1_2_3_2_2', 'first-page': '206', 'volume-title': 'Applied Homogeneous Catalysis with Organometallic Compound, Vol. 1', 'author': 'Brunner H.', 'year': '1996'} / Applied Homogeneous Catalysis with Organometallic Compound, Vol. 1 by Brunner H. (1996)
{'key': 'e_1_2_3_3_2', 'volume-title': 'Asymmetric Catalysis in Organic Synthesis', 'author': 'Noyori R.', 'year': '1994'} / Asymmetric Catalysis in Organic Synthesis by Noyori R. (1994)
10.1002/1521-3757(20020617)114:12<2108::AID-ANGE2108>3.0.CO;2-Z
10.1002/1521-3773(20020617)41:12<2008::AID-ANIE2008>3.0.CO;2-4
{'key': 'e_1_2_3_5_2', 'volume-title': 'Catalytic Asymmetric Synthesis', 'author': 'Ojima I.', 'year': '1993'} / Catalytic Asymmetric Synthesis by Ojima I. (1993)
{'key': 'e_1_2_3_6_2', 'first-page': '961', 'author': 'Claver C.', 'year': '2000', 'journal-title': 'Chem. Commun.'} / Chem. Commun. by Claver C. (2000)
10.1016/S0957-4166(00)86112-1 / Tetrahedron: Asymmetry by Hayashi T. (1992)
Though relatively uncommon diamino ligands in organometallic complexes that are catalytic for hydrogenation were reported. For example
10.1002/ange.19941060504
10.1002/anie.199404971
10.1016/S0957-4166(99)00173-1
10.1021/cr9902897
10.1016/1381-1169(96)00148-3
10.1002/1615-4169(200210)344:9<915::AID-ADSC915>3.0.CO;2-I
{'key': 'e_1_2_3_14_2', 'first-page': '9163', 'volume': '15', 'author': 'Pertici P.', 'year': '1996', 'journal-title': 'Organometallics'} / Organometallics by Pertici P. (1996)
10.1016/S1381-1169(01)00286-2
10.1039/C39910001253
10.1016/0022-328X(92)80121-D
Crystallographic data:1 a Rh CODcomplex C15H28BF4N2Rh M=426.11 g mol−1 yellow prisms 0.28×0.14×0.07 mm monoclinic a=9.1422(2) Å b=10.8050(4) Å c=9.3369(3) Å β=110.243(2)° V=865.34(5) Å3 T=180(2) K space groupP21 Z=2 5542 reflections collected 3400 independent reflections (Rint=0.0286) refinement method: full matrix least squares onF2 finalR1=0.0254 wR2=0.0588 GOF=1.125.1 a Rh NBDcomplex C14H24BF4N2Rh M=410.07 g mol−1 yellow prisms 0.25×0.12×0.12 mm orthorhombic a=9.3033(2) Å b=10.4587(3) Å c=16.7856(5) Å β=90° V=1633.25 Å3 T=180(2) K space groupP212121 Z=4 9724 reflections collected 3359 independent reflections (Rint=0.1154) refinement method: full matrix least squares onF2 finalR1=0.0591 wR2=0.1278 GOF=0.991.1 a Pdcomplex C10H21BF4N2Pd M=362.50 g mol−1 clear prisms 0.30×0.18×0.12 mm orthorhombic a=8.0393(3) Å b=12.8833(4) Å c=13.8562(5) Å β=90° V=1435.12(9) Å3 T=180(2) K space groupP21 Z=2 8364 reflections collected 3190 independent reflections (Rint=0.0319) refinement method: full matrix least squares onF2 finalR1=0.0303 wR2=0.0700 GOF=1.032 crystallographic data is available in the .cif format. CCDC‐193929 (1 a Rh COD) CCDC‐193930 (1 a Rh NBD) and CCDC‐203770 (1 a Pd) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre 12 Union Road Cambridge CB2 1EZ UK; fax: (+44) 1223‐336‐033; or deposit@ccdc.cam.ac.uk).
10.1016/S1381-1169(98)00257-X
10.1002/(SICI)1521-3757(19991216)111:24<3800::AID-ANGE3800>3.0.CO;2-1
10.1002/(SICI)1521-3773(19991216)38:24<3588::AID-ANIE3588>3.0.CO;2-4
10.1039/a902441g
10.1039/b005689h
10.1246/cl.1994.1095
10.1016/S0957-4166(97)00526-0
10.1006/jcat.1999.2584
10.1016/S1381-1169(01)00345-4
10.1021/ar990017q
10.1021/ie0206610
We are grateful to one of the referees for drawing the contrast between the Rh‐diphosphane and Rh‐diamine‐diene catalysts to our attention.
R.Raja J. M.Thomas B. F. G.Johnson M. D.Jones German Patent DE‐10305946 2003and DE‐103059432003.
Accepted theory amongst experts in homogeneous catalysis states that the diene (in this case COD or NBD) are no longer present in the catalyst when it facilitates hydrogenation. But if this were true the catalytic performance of a given organometallic complex would be independent of the initially coordinated diene. This is patently not the case—see Drexler et al. [15a]where RhIhydrogenation catalysts exhibit a thousand fold difference in reactivities on replacing the COD by NBD. In the critical act of catalysis possibly even homogeneously but certainly heterogeneously under the conditions that we employ the diene may still be implicated.[13]This is why we have depicted the as‐prepared heterogeneous catalyst in Figure 3 a and 3 b;
10.1016/S0022-328X(00)00756-7
J. M. Thomas et al. unpublished results.
10.1002/hlca.200390145
10.1039/b003354p

Dates

Type	When
Created	21 years, 11 months ago (Sept. 17, 2003, 10:21 a.m.)
Deposited	1 year, 10 months ago (Oct. 11, 2023, 7:10 a.m.)
Indexed	1 month ago (July 22, 2025, 7:10 a.m.)
Issued	21 years, 11 months ago (Sept. 17, 2003)
Published	21 years, 11 months ago (Sept. 17, 2003)
Published Online	21 years, 11 months ago (Sept. 17, 2003)
Published Print	21 years, 11 months ago (Sept. 22, 2003)

Funders 0

None

BibTeX

@article{Jones_2003, title={Enhancing the Enantioselectivity of Novel Homogeneous Organometallic Hydrogenation Catalysts}, volume={42}, ISSN={1521-3773}, url={http://dx.doi.org/10.1002/anie.200250861}, DOI={10.1002/anie.200250861}, number={36}, journal={Angewandte Chemie International Edition}, publisher={Wiley}, author={Jones, Matthew D. and Raja, Robert and Thomas, John Meurig and Johnson, Brian F. G. and Lewis, Dewi W. and Rouzaud, Jacques and Harris, Kenneth D. M.}, year={2003}, month=sep, pages={4326–4331} }

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