Preparation, structure, and reactivity of nonstabilized organoiron compounds. Implications for iron-catalyzed cross coupling reactions

Journal of the American Chemical Society

Volumn 130, Issue 27, 2008, Pages 8773-8787

  Fürstner, Alois ^a   Martin, Rubén ^a   Krause, Helga ^a   Seidel, Günter ^a   Goddard, Richard ^a   Lehmann, Christian W ^a  

^a MAX PLANCK INSTITUT FÜR KOHLENFORSCHUNG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ARSENIC COMPOUNDS; IRON COMPOUNDS; METALS;

CROSS-COUPLING REACTIONS; ELECTRONICALLY UNSATURATED; HOMOLEPTIC; METAL CENTERS; ORGANOIRON(II) COMPLEXES; OXIDATION STATES; REACTIVITY (CHEMICAL); STABILIZING LIGANDS;

IRON;

ALKYL GROUP; ALLYL COMPOUND; BENZYL DERIVATIVE; GRIGNARD REAGENT; HALIDE; IRON COMPLEX; MAGNESIUM DERIVATIVE; ORGANIC COMPOUND;

ARTICLE; CATALYSIS; CHEMICAL BOND; CHEMICAL REACTION; CHEMICAL STRUCTURE; COMPLEX FORMATION; CROSS COUPLING REACTION; CRYSTAL STRUCTURE; REACTION ANALYSIS; SYNTHESIS;

EID: 46949098763     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja801466t     Document Type: Article

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179. (c) Rosa, P.; Mézailles, N.; Ricard, L.; Mathey, F.; Le Floch, P.; Jean, Y. Angew. Chem., Int. Ed. 2001, 40, 1251.
180. (d) Ellis, J. E.; Chen, Y. S. Organometallics 1989, 8, 1350.
181. (e) Ellis, J. E. Adv. Organomet. Chem. 1990, 31, 1.
182. The structure of 8 has previously been communicated by Jonas; cf. ref 54b. Apparently 8 exhibits polymorphism, since these authors reported a primitive orthorhombic unit cell (Pbcn with a = 12.279(1), b = 13.069(1), and c = 16.336(2) A°. The comparison of the bond lengths between the earlier room temperature structure and the present 100 K structure shows differences around 0.01 to 0.02 Å. Unfortunately no atomic coordinates of the structure published in 1979 are available for a more detailed comparison. However, it is noteworthy that for the previous structure two unit cell edges are halved compared to the present unit cell, while one is doubled. No transformation between the present F-centered and the earlier primitive unit cell was found.
183. n]; cf.: Felkin, H.; Knowles, P. J.; Meunier, B.; Mitschier, A.; Ricard, L.; Weiss, R. J. Chem. Soc., Chem. Commun. 1974, 44.
184. (b) Felkin, H.; Knowles, P. J.; Meunier, B. J. Organomet. Chem. 1978, 146, 151.
185. (c) Burlitch, J. M.; Ulmer, S. W. J. Organomet. Chem. 1969, 19, P21.
186. (d) McVicker, G. B Inorg. Chem. 1975, 14, 2087.
187. n] are also in line with largely covalent intermetallic bonds; cf. ref 31.
188. N2 processes. However, it is not sufficiently active to insert into nonactivated aryl halides under mild conditions; cf.: Collman, J. P. Acc. Chem. Res. 1975, 8, 342.
189. (b) Ellis, J. E. Organometallics 2003, 22, 3322.
190. (c) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry, 2nd ed.; University Science Books: Mill Valley, CA, 1987.
191. 2]Na was reported to react with certain aryl and vinyl halides; cf.: King, R. B. Acc. Chem. Res. 1970, 3, 417.
192. (a) Reviews : Netherton, M. R.; Fu, G. C. Adv. Synth. Catal. 2004, 346, 1525.
193. (b) Frisch, A. C.; Beller, M. Angew. Chem., Int. Ed. 2005, 44, 674.
194. (c) Cárdenas, D. J. Angew. Chem., Int. Ed. 2003, 42, 384.
195. (a) Pasto, D. J.; Hennion, G. F.; Shults, R. H.; Waterhouse, A.; Chou, S.-K. J. Org. Chem. 1976, 41, 3496.
196. (b) Pasto, D. J.; Chou, S.-K.; Waterhouse, A.; Shults, R. H.; Hennion, G. F. J. Org. Chem. 1978, 43, 1385.
197. (c) Hashmi, A. S. K.; Szeimies, G. Chem. Ber. 1994, 127, 1075.
198. 3 through directed delivery of the nucelophile; cf.: Fürstner, A.; Méndez, M. Angew. Chem., Int. Ed. 2003, 42, 5355.
199. (b) For applications of this method in total synthesis, see: Lepage, O.; Kattnig, E.; Fürstner, A. J. Am. Chem. Soc. 2004, 126, 15970.
200. (c) Fürstner, A.; Kattnig, E.; Lepage, O. J. Am. Chem. Soc. 2006, 128, 9194.
201. The fact that tert-halides are inert is somewhat surprising if one assumes that radical intermediates may be involved in such iron-catalyzed processes.
202. Tertiary halides can be cross coupled with certain Grignard reagents in the presence of silver salts by a reaction that is believed to involve radical intermediates; cf.: Tamura, M.; Kochi, J. J. Am. Chem. Soc. 1971, 93, 1483.
203. Early CIDNP experiments suggested the interference of radicals in iron-catalyzed processes; cf. ref 25.
204. For evidence that radical intermediates are involved in the Ni-catalyzed cross coupling reaction of alkyl halides, see:(a) Andersen, T. J.; Jones, G. D.; Vicie, D. A. J. Am. Chem. Soc. 2004, 126, 8100.
205. (b) Phapale, V. B.; Buñuel, E.; García-Iglesias, M.; Cárdenas, D. J. Angew. Chem., Int. Ed. 2007, 46, 8790.
206. For related experiments, see ref 181.
207. For related experiments with cyclopropylmethyl iodide, see: Bedford, R. B.; Betham, M.; Bruce, D. W.; Davis, S. A.; Frost, R. M.; Hird, M. Chem. Commun. 2006, 1398.
208. For the rate constants of cyclopropylmethyl radical ring opening, see: Newcomb, M.; Johnson, C. C.; Manek, B.; Varick, T. R. J. Am. Chem. Soc. 1992, 114, 10915.
209. Fraenkel, G.; Chow, A.; Winchester, W. R. J. Am. Chem. Soc. 1990, 112, 1382.
210. The diallyliron complex 34 was characterized by X-ray crystallography. The data obtained for the sample prepared according to Scheme 9 were identical with those reported in the literature: Smith, J. D.; Hanusa, T. P.; Young, V. G J. Am. Chem. Soc. 2001, 123, 6455.
211. Tris(π-allyl)iron has been briefly mentioned, but a full characterization is missing; cf.: Wilke, G.; Bogdanovic, B.; Hardt, P.; Heimbach, P.; Keim, W.; Kröner, M.; Oberkirch, W.; Tanaka, K.; Steinrücke, E.; Walter, D.; Zimmermann, H. Angew. Chem., Int. Ed. Engl. 1966, 5, 151.
212. 2Mg; cf.: Bogdanović, B.; Huckett, S. C.; Wilczok, U.; Rufínska, A Angew. Chem., Int. Ed. Engl. 1988, 27, 1513.
213. (b) Holle, S.; Jolly, P. W.; Mynott, R.; Salz, R. Z. Naturforsch., B: Anorg. Chem., Org. Chem. 1982, 37, 675.
214. This propensity is believed to be essential for nickel-catalyzed cross coupling of Grignard reagents with alkyl halides; see: Terao, J.; Kambe, N. Bull. Chem. Soc. Jpn. 2006, 79, 663.
215. (a) For reference data, see inter alia: ref 77a.
216. (b) Faller, J. W.; Johnson, B. V.; Dryja, T. P. J. Organomet. Chem. 1974, 65, 395.
217. (c) Faller, J. W.; Chen, C. G.; Mattina, M. J.; Jakubowski, A. J. Organomet. Chem. 1973, 52, 361.
218. Note that the reaction of a Jonas-type lithium ferrate complex with an organic halide formally constitutes a σ-bond metathesis and not a conventional oxidative insertion.
219. (a) Similar experiments were reported by Lehmkuhl et al., even though no crystal structures of the iron complexes could be obtained. These authors show that 7 is equally amenable to oxidative insertion into vinyl chlorides: Lehmkuhl, H.; Mehler, G.; Benn, R.; Rufínska, A.; Schroth, G.; Krüger, C.; Raabe, E. Chem. Ber. 1987, 120, 1987.
220. (b) Benn, R.; Brenneke, H.; Frings, A.; Lehmkuhl, H.; Mehler, G.; Rufinska, A.; Wildt, T. J. Am. Chem. Soc. 1988, 110, 5661.
221. (c) For an alternative synthesis and use of such complexes as catalysts in Kharasch-type homocoupling reactions, see: Felkin, H.; Meunier, B. J. Organomet. Chem. 1978, 146, 169.
222. (a) Hill, D. H.; Sen, A. J. Am. Chem. Soc. 1988, 110, 1650.
223. (b) Hill, D. H.; Parvez, M. A.; Sen, A. J. Am. Chem. Soc. 1994, 116, 2889.
224. (a) Alkyl iron complexes stabilized by nitrogen-based ligands are known in the literature; see ref 29 and the following for leading references and literature cited therein: Bart, S. C.; Hawrelak, E. J.; Schmisseur, A. K.; Lobkovsky, E.; Chirik, P. J. Organometallics 2004, 23, 237.
225. (b) Lau, W.; Huffman, J. C.; Kochi, J. K. Organometallics 1982, 1, 155.
226. Related disproportionation reactions were also suggested by Hayashi to participate in iron-catalyzed C-C bond formations; cf. ref 19b.
227. Because of the volatility of hexadiene, its presence could only be confirmed by GC/MS.
228. For a similar conclusion, proposing the generation of radicals by homolysis of a diorganoiron intermediate primarily formed, see ref 18i.
229. According to GC/MS, these byproducts show mass peaks of mlz = 134, 136, and 212, which formally correspond to [Cp*-2], [Cp*], and [Cp*+Ph], respectively. The structures of these compounds have not been analyzed any further.
230. Additional support comes from our previous observation that finely dispersed Rieke iron slowly dissolves on exposure to the solution of a Grignard reagent to afford a dark brown and catalytically competent iron species of unknown constitution; cf. ref 14a.
231. Jonas, K.; Koepe, G.; Krüger, C. Angew. Chem., Int. Ed. Engl. 1986, 25, 923.
232. Attempted reaction of methyl 4-bromocrotonate with PhLi in the presence of catalytic amounts of complex 8 affords bromobenzene as the major product.