USOO6451937B1 (12) United States Patent (10) Patent No.: US 6,451,937 B1 Hartwig et al. (45) Date of Patent: Sep. 17, 2002 (54) SELECTIVE, CATALYTIC, THERMAL “Formation and chemistry of the transient 17-electron com FUNCTIONALIZATION OF PRIMARY C-H pounds CpFe(CO)L (L=PMePh, PPh).” by Inga Kuksis, HYDROCARBON BONDS Michael C. Baird, Journal of Organometallic Chemistry 527 (1997) pp. 137–143. (75) Inventors: John F. Hartwig, New Haven, CT “Iron-rhodium complexes with a Single bridging diphos (US); Thomas Carl Semple, phine ligand: the crystal Structured of Friendswood, TX (US); Huiyuan Chen, CpFe(u-CO)(u-dppm)Rhill.” by Ian Mansfield, Nagwa New Haven, CT (US) Nawar, Anthony K. Smith, Nicola C. Tong, Journal of Organometallic Chemistry 525(1996) pp. 255–258. (73) Assignees: Shell Oil Company, Houston, TX “Transition-Metal Boryl Complexes: Structure and Reac (US); Yale University, New Haven, CT tivity of CpFe(CO).Bcat and CpFe(CO). BPh.” John F. (US) Hartwig and Susan Huber, J. Am. Chem. Soc. 115 (1993) pp. 4908-4909. (*) Notice: Subject to any disclaimer, the term of this “Selective Functionalization of Alkanes by TransitionMetal patent is extended or adjusted under 35 Boryl Complexes,” by Karen M. Waltz and John F. Hartwig, U.S.C. 154(b) by 0 days. Science, vol. 277, Jul 11, 1997. “Stoichiometric and Catalytic B-C Bond Formation from (21) Appl. No.: 09/516,897 Unactivated Hydrocarbons and Boranes,” by Carl N. Iverson and Milton R. Smith, III, J. Am. Chem. Soc., 121 (1999), pp. (22) Filed: Mar. 1, 2000 7696-7697. “First synthesis of bis1,2,3triazolo 1,5-b;5,1'-f1,3,6 (51) Int. Cl." ............................ C08F 4/44; CO8F 10/00; thiadiazepine derivatives by 2+1 condensation of 1,2, CO7F 15/00 3-thiadiazoles with vicinal diamines,” by Natalya N. (52) U.S. Cl. ........................... 526/126; 526/282; 556/9; Volkova, Evgeniy V. Tarasov, Wim Dehaen, and Vasiliy A. 556/13; 556/12; 556/11 Bakulev, Received (in Cambridge, UK) Sep. 16, 1999, (58) Field of Search ................................ 556/9, 13, 12, Accepted Oct. 8, 1999. 556/11, 126, 282 “Reactions of Rhodium(v) Hydrido-Silyl Complexes with Butyl-lithium and with Lithium Triethylhydridoborate,” by (56) References Cited Jose Ruiz, Brian E. Mann, Catriona M. Spencer, Brian F. U.S. PATENT DOCUMENTS Taylor, and Peter M. Maitlis, J. Chem. Soc. Dalton Trans (1987) pp. 1963–1966. 5,059,701 A 10/1991 Keipert ........................ 556/13 “Organoboron Compounds. Part V. The Hydrolysis of 5,089,536 A 2/1992 Palazzotto ................... 522/16 Cyclic Phenylboronates,” by R. A. Bowie and O. C. Mus 5,321,106 A 6/1994 LaPointe .......... ... 526/126 5,527,929 A 6/1996 Timmers et al. ............... 556/7 grave, pp. 3945-3948. 5.532,394 A 7/1996 Rosen et al. .................. 556/11 “(m-Pentamethylcyclopentadienyl)Rhodium and -Iridium 5,539,068 A 7/1996 Devore et al. .... ... 526/126 Compounds.” Submitted by C. White, A. Yates, and P. M. 5,541,349 A 7/1996 Wilson et al. ................ 556/10 Maitlis, Checked by D. M. Heinekey, Transition Metal 5,543,480 A 8/1996 Patton et al. ........ ... 526/126 Organometallics and Ligands, pp. 228-234. 5,616,664 A 4/1997 Timmers et al. ..... ... 526/127 Tetrahydrido(m-Pentamethylcyclopentadienyl)Iridium, 5,621,126 A 4/1997 Canich et al. ................. 556/9 Submitted by Thomas M. Gilbert and Robert G. Bergman, 5,703,187 A 12/1997 Timmers .......... ... 526/282 Checked by Joseph S. Merola, Transition Metal Polyhydride 5,770.538 A 6/1998 Devore et al............... 502/117 Complexes, pp. 19-22. OTHER PUBLICATIONS “A Study of Hydroboration of Alkenes and Alkynes with Pinacolborane Catalyzed by transition Metals,” by Schubert U.S. patent application Ser. No. 09/516,896, Hartwig et al., Pereira and Morris Srebnik, Tetrahedron Letters, vol. 37, filed Mar. 1, 2000. No. 19, (1996) pp. 3283–3286. “Pentamethylcyclopentadienyl-rhodium and -iridium Com "Facile Intermolecular Activation of C-H Bonds in Methane plexes. Part VI. L-Arene, JL-Cyclohexadienyl, and JL-Pyr and Other Hydrocarbons and Si-H Bonds in Silanes with the rolyl Complexes,” by C. White and P. M. Maitlis, J. Chem. Ir(III) Complex Cp*(PMe)Ir(CH4)(OTf).” by Peter Burger Soc. (A), 1971, pp. 3322–3326. and Robert G. Bergman, J. Am. Chem. Soc., 115, (1993) pp. “Pentamethylcyclopentadienyl-rhodium and -iridium and 10462-10463. iridium Halides, Part II. Reactions with Mono-, Di-, and Tri-olefins,” by K. Moseley, J. W. Kang, and P. M. Maitlis, (List continued on next page.) J. Chem. Soc. (A), 1970, pp. 2875-2883. “Thermal Substitution reactions of the heterodinuclear com Primary Examiner Deborah C. Lambkin plex CpFe(CO)Co(CO), with phosphorus ligands,” by (57) ABSTRACT Xiaoqing Song, Theodore L. Brown, Inorganica Chimica Acta 242 (1996) pp. 271-279. A proceSS for the catalytic coupling of aliphatic or alkyl “The reaction of CpFe(CO).X(X=Cl, Br, I) with phosphines branched alicyclic hydrocarbons with a functionalizing catalyzed by CpFe(CO): evidence for an electron trans reagent under thermal conditions to Selectively functionalize fer chain catalysis mechanism,” by Stephen L. Gipson, the hydrocarbon at its primary C-H site. Ling-Kang Liu, Raul U. Soliz, Journal of Organometallic Chemistry 526 (1996) pp. 393-395. 106 Claims, No Drawings US 6,451,937 B1 Page 2 OTHER PUBLICATIONS “Synthesis of Boryl Metal Complexes with Additional Ago stic Stabilization by Hydroboration of Fischer Carbyne “C-H Bond Activation by a rare Cationic Iridium Dinitrogen Complex. An Important Electronic Effect in the Chemistry Complexes,” by H. Wadepohl, U. Arnold, and H. Pritzkow, of the Hydridotris(pyrazolyl)borate Ligand,” by David M. Angew. Chem. Int. Ed. Engl., 36, No. 9, (1997) pp. 974-976. Tellers and Robert G. Bergman, J. Am. Chem. Soc., 122 “Five-Coordinate Ruthenium (II) and Osmium(II) Boryl (2000) pp. 954-955. Complexes,” by Geoffrey J. Irvine, Warren R. Roper, and L. “Typical Procedure for the Hydroboration of Alkynes Using James Wright, Organometallics, 16 (1997) pp. 2291-2296. Pinacolborane,” J. Org. Chem., vol. 57, No. 12, (1992) pp. “Transition-Metal-Catalyzed Addition of Catecholborane 3484-3485. to C-Substituted Vinylarenes: Hydroboration vs Dehydro “Synthese, Struktur and Reaktivität der Ferriophosphonium genative Borylation,” by Stephen A. Westcott and Todd B. Salze CpFe(CO)(L)(PPhCHR)BF(L=CO, CHCN, Marden, Organometallics, 12 (1993) pp.975-979. P"Bus; R'-PH, CN, COOEt, PPh, SiMe); Kristallstruk “Synthesis and molecular Structure of the paramagnetic turen VO CpFe(CO)PPhCHSiMeBF und Co(II) bis(boryl) complex Co(PMe)(Bcat) cat=1, CpFe(PPhCHPh)CpFe(CO)(u-CO).” by Christian 2-O.C.H.).” by Chaoyang Dai, Graham Stringer, John F. Klasen, Ingo-Peter Lorenz, Siegbert Schmid und Georg Corrigan, Nicholas J. Taylor, Todd B. Marder, and Nicholas Beuter, Journal of Organometallic Chemistry, 428 (1992) C. Norman, Journal of Organometallic Chemistry, 513 pp. 363-378. (1996) pp. 273–275. “Synthesis and Characterization of Rhodium(I) Boryl and Rhodium (III) Tris(Boryl) Compounds: Molecular Struc “Reactivity of Organoplatinum Complexes with tures of(PMe), Rh(B(cat)) and fac-(PMe)Rh(B(cat)) CHOB-BOC.H. Syntheses of a Platinum Diboryl (cat=1,2–OCH), by Chaoyang Dai, Graham Stringer, Complex with, and without, Metathesis of Boron-Boron and Todd B. Marder, Andrew J. Scott, William Clegg, and Metal-Carbon Bonds,” by Carl N. Iverson and Milton R. Nicholas C. Norman, Inorg. Chem., 36 (1997) pp. 272-273. Smith, III, J. Am. Chem. Soc., 117 (1995) pp. 4403-4404. Oxidative Addition of boron-boron, boron-chlorine and “Synthesis of endo-CpTaH(BOCH) and boron-bromine bonds to platinum(0), by W. Clegg, F.J. exo-cp-TaH(BOCH): Regioisomers of the First Tanta Lawlor, G. Lesley, T.B. Marder, N.C.Norman, A.G.Orpen, lum Boryl Complexes,” by Dean R. Lantero, Douglas H. M.J. Quayle, C.R.Rice, A.J.Scott, and F.E.S. Souza, Journal Motry, Donald L. Ward, and Milton R. Smith, III, J. Am. of Organomettalic Chemistry 550 (1998) pp. 183-192. Chem. Soc., 116 (1994) pp. 10811–10812. “Boron-boron bond oxidative addition to rhodium(I) and “C-H Activation and Functionalization of Unsaturated iridium(I) centres,” by W. Clegg, F.J. Lawlor, T.B. Marder, Hydrocarbons by Transition-Metal Boryl Complexes,” by P. Nguyen, N.C.Norman, A.G. Orpen, M.J. Quayle, Karen M. Waltz, Clare N. Muhoro, and J. F. Hartwig, C.R. Rice, E.G.Robins, A.J. Scott, F.E.S. Souza, G. Stringer, Organometallics 1999, 18, pp. 3383-3393. and G.R. Whittell, J. Chem. Soc. Dalton Trans., 1998 pp. 301-309. “Functionalization of Alkanes by Isolated Transition Metal “Reactions of catecholborane wit iridium complexes: Boryl Complexes,” by Karen M. Waltz II and John F. molecular structure of trans-IrHCI(CO)(Bcat) (PPh3).” Hartwig, J. Am. Chem. Soc. 2000, 122, pp. 11358–11369. Stephen A. Westcott, Todd B. Marder, R. Thomas Baker, and “Reactivity of Tungstenocene with B-B and B-H Bonds Joseph C. Calabrese, Canadian Journal of Chemistry, vol versus C-H Bonds,” by John F. Hartwig and Xiaoming He, 71, No. 7, Jul. 1993, pp. 930-936. Angew. Chem. Int. Ed, Engl. 1996, 35, No. 3, pp. 315-317. US 6,451,937 B1 1 2 SELECTIVE, CATALYTIC, THERMAL or unsubstituted electron donor moiety which does not FUNCTIONALIZATION OF PRIMARY C-H dissociate under thermal reaction conditions, wherein HYDROCARBON BONDS Said moiety (i) lacks aromatic C-H bonds on the moiety directly 1. FIELD OF THE INVENTION bonded to the transition metal, or (ii) contains sterically hindered aromatic C-H bonds The field of the invention pertains to the selective func on the moiety directly bonded to the transition metal; tionalizing of a hydrocarbon at its primary C-H site by and thermally reacting a functionalizing reagent and the hydro c) a Source of ligands capable of formally donating an carbon in the presence of an transition metal catalyst.