Journal of the American Chemical Society
Page 6 of 8
(
5) Murahashi, S.-I.; Takaya, H. Low-valent ruthenium and iridium
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
hydride complex as alternatives to lewis acid and base catalysts. Acc.
Chem. Res. 2000, 33, 225-233.
CONCLUSIONS
(
6) Kukushkin, V. Y.; Pombeiro, A. J. L. Additions to metal-activated
organonitriles. Chem. Rev. Chem. Rev. 2002, 102, 1771-1802.
7) Chin, J.; Kim, J. H. Catalytic hydration of acrylonitrile to acryla-
The above findings illustrate that the newly synthesized “do-
nor-acceptor”-type catalyst 2c is superior towards hydration
of nitriles and cyanohydrins from two characteristics. First, it
can promote nitrile hydration at room temperature with good
turnover numbers. Second, due to its high activity at ambient
temperature, hydration of cyanohydrins can be achieved by 2c
with high efficiency. These attributes distinguish catalyst 2c
not only from the most effective nitrile hydration catalysts
reported to date, such as Parkins catalyst (1a), but also from
the other types of ferrocenyl-phosphine platinum catalysts 2a,
(
mide under mild conditions. Angew. Chem. Int. Ed. 1990, 29, 523-525.
(8) Kim, J. H.; Britten, J.; Chin, J. Kinetics and mechanism of a Co
(III) complex catalyzed hydration of nitriles. J. Am. Chem. Soc. 1993,
1
(
15, 3618-3622.
9) Breno, K. L.; Pluth, M. D.; Tyler, D. R. Organometallic chemistry
in aqueous solution, hydration of nitriles to amides catalyzed by a
+
2 2
water-soluble molybdocene, (MeCp) Mo(OH)(H O) . Organometal-
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
lics 2003, 22, 1203-1211.
(
10) Takaya, H.; Yoshida, K.; Isozaki, K.; Terai, H.; Murahashi, S.-I.
2
b, 2d and 2e, which have likewise surpassed 1a in the hydra-
Transition-metal-based lewis acid and base ambiphilic catalysts of
Iridium hydride complexes: multicomponent synthesis of glutarimides.
Angew. Chem. Int. Ed. 2003, 42, 3302-3304.
(11) Goto, A.; Endo, K.; Saito, S. Rh(I)-catalyzed hydration of orga-
nonitriles under ambient conditions. Angew Chem Int Ed. 2008, 47,
tion of both nitriles and cyanohydrins. Ongoing research pur-
suits in this filed include discovering more practical and inex-
pensive catalysts that can be utilized in industry, and the in-
corporation of chiral bidentate phosphine ligands in related
new “donor-acceptor”-type catalysts for the development of
asymmetric protocols by the means of nitrile and cyanohydrin
hydrations.
3
607-3609.
(
12) Charlotte, M.; Djoman, K. B.; Ajjou, A. N. The hydration of
nitriles catalyzed by water solubale rhodium complexes. Tetrahedron
Lett. 2000, 41, 4845-4849.
(
13) Yamaguchi, K.; Matsushita, M.; Mizuno, N. Efficient hydration
ASSOCIATED CONTENT
Supporting Information.
The Supporting Information is available free of charge on the
ACS Publications website at DOI:
Experimental procedures and characterization data ( H and
NMR, HRMS) for all new compounds (PDF)
Crystallographic information for 2a (CIF)
Crystallographic information for 2b (CIF)
Crystallographic information for 2b (CIF)
of nitriles to amides in water, catalyzed by ruthenium hydroxide sup-
ported on alumina. Angew. Chem. Int. Ed. 2004, 43, 1576-1580.
(14) Fung, W. K.; Huang, X.; Man, M. L.; Ng, S. M.; Hung, M. U.;
Lin, Z. Y.; Lau, C. P. Dihydrogen-bond-promoted catalysis catalytic
5
1
13
hydration of nitriles with indenylruthenium hydride complex ( -
C
9 7
C H )Ru(dppm)H. J. Am. Chem. Soc. 2003, 125, 11539-11544.
(
15) Oshiki, T.; Yamashita, H.; Sawada, K.; Utsunomiya, M.;
Takahashi, K.; Takai, K. Dramatic rate acceleration by a diphenyl-2-
pyridylphosphine ligand in the hydration of nitriles catalyzed by
Ru(acac)
16) Bennett, M. A.; Yoshida, T. Homogeneous catalyzed hydration
of nitriles to carboxamides. J. Am. Chem. Soc. 1973, 95, 3030-3031.
17) Bennett, M. A.; Yoshida, T. Synthesis and reactivity of zerova-
lent platinum complexes of short-lived cyclic alkynes. Formation of
monomeric platinum(II) hydroxo-, methoxo- -carbon-bonded
2
complexes. Organometallics 2005, 24, 6287-6290.
(
AUTHOR INFORMATION
Corresponding Author
(
*
*
complexes by oxidative addition reactions with water, methanol, and
activated hydrocarbons and catalysis of hydration of nitriles to amides.
J. Am. Chem. Soc. 1978, 100, 1750-1759.
(18) Jensen, C. M.; Trogler, W. C. Kinetic and mechanism of nitrile
hydration catalyzed by unhindered hydridobis(phosphine)platinum(II)
complexes. Regioselective hydration of acrylonitrile. J. Am. Chem.
Soc. 1986, 108, 723-729.
Author Contributions
§
These authors contributed equally.
ACKNOWLEDGMENT
We wish to thank Shenzhen Nobel Prize Scientists Laboratory
Project (grant C17783101), the Gordon and Betty Moore Founda-
tion, the King Faud University of Petroleum and Minerals and
Caltech for financial support. Ms. Julie Hofstra is acknowledged
for assistance in solving the X-ray structure of 2a−c. We thank Dr.
Michael Takase and Mr. Larry Henling for acquiring the X-ray
diffraction data for catalysts 2a−c. Dr. Tonia Ahmed, Dr. Arthur
Han and Professor Dr. Søren Kramer are acknowledged for revis-
ing the manuscript.
(19) Singh, K.; Sarbajna, A.; Dutta, I.; Pandey, P.; Bera, J. K.
II
Hemilability-driven water activation: A Ni catalyst for base-free
hydration of nitriles to amides. Chem. Eur. J. 2017, 23, 7761-7771.
(20) Parkins, A. W. Catalytic hydration of nitriles to amides: plati-
num-containing catalyst offers new opportunity. Platinum Metal Rev.
1
995, 40, 169-174.
(
21) Ghaffar, T.; Parkins, A. W. A new homogeneous platinum cata-
lyst for the hydrolysis of nitriles. Tetrahedron Lett. 1995, 36, 8657-
8660.
(
22) Cadierno, V. Synthetic application of the Parkins nitrile hydra-
tion catalyst [PtH{(PMe O) H}(PMe OH)]: a review. Appl. Sci. 2015,
, 380-401.
23) Mercado-Marin, E. V.; Garcia-Reynaga, P.; Romminger, S.;
2
2
2
REFERENCES
5
(
(
1) Dong, G. B.; Teo, P. L.; Wickens, Z. K.; Grubbs, R. H. Primary
Pimenta, E. F.; Romney, D. K.; Lodewyk, M. W.; Williams, D. E.;
Andersen, R. J.; Miller, S. J.; Tantillos, D. J.; Berlinck, R. G. S.; Sar-
pong, R. Total synthesis and isolation of citrinalin and cyclopiamine
congeners. Nature 2014, 509, 318-324.
alcohols from terminal olefins: formal anti-Markovnikov hydration
via triple relay catalysis. Science 2011, 333, 1609–1612.
(
2) Haggin, J. Chemists seek greater recognition for catalysis. Chem.
Eng. News 1993, 71, 23-27.
3) Guo, J. Y.; Teo, P. L. Anti-Markovnikov oxidation and hydration
of terminal olefins. Dalton Trans. 2014, 43, 6952-6964.
4) Mathias, L. J.; Vaidya, R. A.; Canterberry, J. B. Nylon 6-a simple,
safe synthesis of a tough commercial polymer. J. Chem. Educ. 1984,
1, 805-807.
(
24) Herzon, S. B.; Myers, A. G. Enantioselective synthesis of Steph-
(
acidin B. J. Am. Chem. Soc. 2005, 127, 5342-5344.
(25) Ahmed, T. J.; Fox, B. R.; Knapp, S. M. M.; Yelle, R. B.; Juliette,
J. J.; Tyler, D. R. Investigation of the reactivity of Pt phosphinito and
molybdocene nitrile hydration catalysts with cyanohydrins. Inorg.
Chem. 2009, 48, 7828-7837.
(
6
ACS Paragon Plus Environment