Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Patent
1999-10-06
2000-08-08
O'Sullivan, Peter
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
544159, 544165, 544167, 548572, 548575, 548578, 560 25, 560115, 560158, 564 89, 564 90, 564238, C07C27916, C07C27918, C07C27924, C07C27120, C07C30340
Patent
active
061004286
ABSTRACT:
An improved method for guanylating amines is provided. Broadly, the amines are reacted with a guanylating agent in the presence of a nickel catalyst. Preferably, the nickel catalyst comprises nickel in the zero oxidation state. Suitable nickel(0) catalysts are derived from nickel-boride alloys, nickel-phosphide alloys, aluminum-nickel alloys, nickel on kieselguhr, and nickel on silica/alumina catalysts. Preferred guanylating agents are thioureas and isothioureas. In one embodiment, protecting groups are selectively attached to the guanylating agents to yield particular substituted guanidines. The preferred protecting groups are Boc groups, Cbz groups, and arylsulfonyl groups. The reactions are particularly well suited for guanylating primary and secondary amines. The methods of the invention can be carried out under ambient conditions to provide high yields of the corresponding guanidines, with the nickel catalyst being essentially completely recoverable for reuse.
REFERENCES:
patent: 3960949 (1976-06-01), Ahrens et al.
Lai, B., et al.; Tetrahedron Lett., 37, pp. 2483-2486, 1996.
Su, W. Synth. Commun., 26, pp. 407-413, 1996.
Kent, D.R., et al.; Tetrahedron Lett., 37, pp. 8711-8714, 1996.
Monache, G.D., et al.; J. Med. Chem., 36, pp. 2956-2963, 1993.
Smith, G.B.L.; J. Am. Chem. Soc., 51, pp. 476-479, 1929.
Phillips, R., et al.; J. Am. Chem. Soc., 45, pp. 1755-1757, 1923.
Lecher, H., et al.; Chem. Ber., 56, pp. 1326-1330, 1923.
Levallet, C., et al.; Tetrahedron, 53, pp. 5291-5304, 1997.
Kim, K.S., et al.; Tetrahedron Lett., 34, pp. 7677-7680, 1993.
Ramadas, K., et al.; Tetrahedron Lett., 36, pp. 2841-2844, 1995.
Youg, Y.F., et al.; J. Org. Chem., 62, pp. 1540-1542, 1997.
Poss, M.A., et al.; Tetrahedron Lett., 33, pp. 5933-5936, 1992.
Manley, P.W., et al.; J. Med. Chem., 35, pp. 2327-2340, 1992.
Olken, N.M., et al.; J. Med. Chem., 35, pp. 1137-1144, 1992.
Farrario, F., et al.; Synthetic Commun., 21, pp. 99-105, 1991.
Rasmussen, C.R., et al.; Synthesis, pp. 456-459, 1988.
Muller, G.W., et al.; J. Med. Chem., 35, pp. 740-743, 1992.
Kim, K., et al.; Tetrahedron Lett., 29, pp. 3183-3186, 1988.
Miller, A.E., et al.; Synthesis, pp. 777-779, 1986.
Maryanoff, C.A., et al.; J. Org. Chem., 51, pp. 1882-1884, 1986.
Bernatowicz, M.S., et al.; Synth. Commun. 23, pp. 657-661, 1993.
Bernatowicz, M.S., et al.; Tetrahedron Lett., 34, pp. 3389-3392, 1993.
Bernatowicz, M.S., et al.; J. Org. Chem., 57, pp. 2497-2502, 1992.
Katrizky, A.R., et al.; Synth. Commun., 25, pp. 1173-1186, 1995.
Feichtinger, K., et al.; J. Org. Chem., 63, pp. 3804-3805, 1998.
Khurana, J.M., et al.; Organic Preparations and Procedures Intl, 29, pp. 1-32, 1997.
Ni, Z-J, et al.; J. Org. Chem, 56, pp. 4035-4042, 1991.
New Developments in Organonickel Chemistry. Symposia-in-Print graphical abstracts, Tetrahedron, 54, pp. 1021-1299, 1988.
Bhat Laxminarayan
Georg Gunda I.
O'Sullivan Peter
The University of Kansas
LandOfFree
Nickel promoted guanylation of amines with isothioureas and thio does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Nickel promoted guanylation of amines with isothioureas and thio, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Nickel promoted guanylation of amines with isothioureas and thio will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-1151550