Synthesis of Functionalized Benzylsilanes from Arylzinc Compounds and (Iodomethyl)trimethylsilane by Means of a Novel Rh Catalysis Hideki Takahashi, Kabir M. Hossain, Yasushi Nishihara, Takanori Shibata, and Kentaro Takagi* Department of Chemistry, Faculty of Science, Okayama UniVersity, Tsushima, Okayama 700-8530, Japan
[email protected] ReceiVed October 7, 2005
The catalytic activity of a Rh complex in cross-coupling between ArZnI and TMSCH2I was examined in which the Rh complex, generated in situ from [RhCl(1,5-cyclooctadiene)]2 and 1,1′-bis(diphenylphosphino)ferrocene, exhibited excellent catalytic activity for the production of various functionalized benzylsilanes in good yields. From 31P NMR studies of various solutions containing several of the reaction components, confirmation of the rapid and quantitative transfer of aryl groups from ArZnI to the Rh complex to form arylrhodium species was ascertained. A catalytic cycle, commencing with the transmetalation, was thus proposed for the reaction.
Introduction Pd- or Ni-catalyzed cross-coupling of carbon electrophiles R+ from aryl, alkenyl, or alkynyl halides with organometallic compounds of B, Si, Sn, Zn, and so on, is one of the most useful methods for constructing carbon-carbon bonds in organic synthesis.1 In contrast to the thoroughly investigated Pd or Ni catalysis, the catalytic activity of other transition metals,2 including Rh,3 has been explored to a far less extent. The peculiar nature of Rh-complex catalysis, from the context that not only the common catalytic cycle commencing with oxidative addition but also one commencing with transmetalation are allowed, does deem it noteworthy (path A vs path B of Figure 1).3b,4 Furthermore, the excellent catalytic activity of Rh has (1) For review, see: (a) Metal-Catalyzed Cross-Coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: Weinheim, Germany, 1998. (b) Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E., Ed.; John Wiley & Sons: New York, 2002. (c) Tsuji, J. Palladium Reagents and Catalysis: InnoVation in Organic Synthesis; John Wiley & Sons: New York, 1995. (2) For review, see: (a) Shinokubo, H.; Oshima, K. Eur. J. Org. Chem. 2004, 2081-2091. (b) Beletskaya, I. P.; Cheprakov, A. V. Coord. Chem. ReV. 2004, 248, 2337-2364. (c) Fuerstner, A.; Martin, R. Chem. Lett. 2005, 34, 624-629. (3) (a) Larock, R. C.; Hershberger, S. S. J. Organomet. Chem. 1982, 225, 31-41. (b) Larock, R. C.; Narayanan, K.; Hershberger, S. S. J. Org. Chem. 1983, 48, 4377-4380. (c) Andrianome, M.; Delmond, B. J. Org. Chem. 1988, 53, 542-545. (d) Andrianome, M.; Haberle, K.; Delmond, B. Tetrahedron 1989, 45, 1079-1088. (e) Hossain, K. M.; Takagi, K. Chem. Lett. 1999, 1241-1242. (f) Ueura, K.; Satoh, T.; Miura, M. Org. Lett. 2005, 7, 2229-2231. (g) Evans, P. A.; Uraguchi, D. J. Am. Chem. Soc. 2003, 125, 7158-7159. (h) Evans, P. A.; Leahy, D. K. J. Am. Chem. Soc. 2003, 125, 8974-8975.
been realized recently in other types of cross-coupling of R+ from carbonyl compounds or conjugated enones with arylmetallic compounds of B, Si, Bi, Ti, or Zn, where transmetalation has been known to be an essential step in the catalytic cycle.5 From consideration of this phenomenon, it was envisaged that certain reactions, hitherto unsatisfactory results with Pd or Ni catalysis, may be affected by making use of a Rh catalyst when R+ and/or organometallic compounds are appropriate for the reaction via path A. Among such reactions, the cross-coupling of arylzinc compounds with silylmethyl halides attracted our attention (Figure 2), as arylzinc compounds are prepared readily from aryl iodides and zinc powder with 100% atom efficiency,6 and of which some are known to form Rh-Ar complexes.7 Silylmethyl halides exhibit enhanced reactivity to Rh in oxidative addition, probably through a nucleophilic displacement (4) (a) Schwartz, J.; Hart, D. W.; Holden, J. L. J. Am. Chem. Soc. 1972, 94, 9269-9271. (b) Semmelhack, M. F.; Ryono, L. Tetrahedron Lett. 1973, 14, 2967-2970. (c) Hegedus, L. S.; Kendall, P. M.; Lo, S. M.; Sheats, J. R. J. Am. Chem. Soc. 1975, 97, 5448-5452. (d) Fanizzi, F. P.; Sunley, G. J.; Maitlis, P. M. J. Organomet. Chem. 1987, 330, C31-C32. (5) For review, see: (a) Fagnou, K.; Lautens, M. Chem. ReV. 2003, 103, 169-196. (b) Hayashi, T.; Yamasaki, K. Chem. ReV. 2003, 103, 28292844. (6) For our synthesis of arylzinc compounds, see: (a) Takagi, K. Chem. Lett. 1993, 469-472. (b) Ogawa, Y.; Saiga, A.; Mori, M.; Shibata, T.; Takagi, K. J. Org. Chem. 2000, 65, 1031-1036. (c) Ikegami, R.; Koresawa, A.; Shibata, T.; Takagi, K. J. Org. Chem. 2003, 68, 2195-2199. Except for Zn, simple substances of other metals such as B, Si, Sn, Bi, or Ti are not applicable to the synthesis of arylmetal compounds from aryl halides as metallic sources. (7) Krug, C.; Hartwig, J. F. J. Am. Chem. Soc. 2002, 124, 1674-1679.
10.1021/jo0520994 CCC: $33.50 © 2006 American Chemical Society
Published on Web 12/14/2005
J. Org. Chem. 2006, 71, 671-675
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FIGURE 1. Two catalytic cycles for transition-metal-catalyzed cross-coupling. TABLE 1. Catalytic Synthesis of Benzylsilane 3aa
FIGURE 2. New entry in a synthetic method of functionalized benzylsilanes.
mechanism,8,9 owing to the presence of a Si substituent at the R position, and lack undesirable side reactions such as the β elimination of the resulting oxidative adducts. Results and Discussion A reaction solution composed of phenylzinc iodide (1a; 1.2 equiv), (iodomethyl)trimethylsilane (2; 1.0 equiv), and a Rh catalyst (5-10 mol %) in N,N,N′,N′-tetramethylurea (TMU) was stirred at 40 °C for 6 h under nitrogen (Table 1). Throughout this study, Rh catalysts were prepared in situ from [RhCl(cod)]2 (cod ) 1,5-cyclooctadiene) and various phosphorus ligands (Rh/P ) 1:2), among which Rh-dppf [dppf ) 1,1′-bis(diphenylphosphino)ferrocene] exhibited excellent catalytic activity in the reaction, giving the desired coupling product 3a in high yield (entry 1). Under the catalysis by Rh-dppf, the reaction also took place smoothly at ambient temperature, requiring 10 mol % of the catalyst (entry 2). Phosphorus ligands such as P(t-Bu)3 and 2-(di-tert-butylphosphino)biphenyl gave the reactive Rh catalyst, but the selectivity was inferior to that of Rh-dppf, as biphenyl was produced in 31 and 40% yields, respectively, along with the desired product (entries 5 and 6). Other Rh catalysts, including the Wilkinson complex, were less effective, and the desired reaction took place slowly, if at all (entries 3, 4, and 7-9). Moreover, neither Pd nor Ni complexes, even ones containing dppf or P(t-Bu)3, showed catalytic activity for this reaction (entries 12-15). As the reaction solvent, DMF was also suitable (entry 10), but 2-methoxyethyl ether was less effective than TMU (entry 11). (Chloromethyl)trimethylsilane could not replace 2 under the examined conditions. Various arylzinc compounds containing such functional groups as CN, (8) Concerning the accelerating effect of R-silyl substituents on the reactivity of alkyl electrophiles for nucleophilic substitution reactions, see for example: (a) Oh, H. K.; Shin, C. H.; Lee, I. J. Chem. Soc., Perkin Trans. 2 1993, 2411-2414. (b) Apeloig, Y.; Biton, R.; Abu-Freih, A. J. Am. Chem. Soc. 1993, 115, 2522-2523. (9) Concerning the SN2 mechanism for oxidative addition of alkyl electrophiles to Rh(I), see for example: (a) Chauby, V.; Daran, J.-C.; SerraLe Berre, C.; Malbosc, F.; Kalck, P.; Gonzalez, O. D.; Haslam, C. E.; Haynes, A. Inorg. Chem. 2002, 41, 3280-3290. (b) Ellis, P. R.; Pearson, J. M.; Haynes, A.; Adams, H.; Bailey, N. A.; Maitlis, P. M. Organometallics 1994, 13, 3215-3226.
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entry
catalyst
temp (°C)
yieldb (%)
1 2 3 4 5 6 7 8 9 10e 11f 12 13 14 15
1:2 [RhCl(cod)]2/dppf 1:2 [RhCl(cod)]2/dppf 1:2 [RhCl(cod)]2/PPh3 1:2 [RhCl(cod)]2/ttmppc 1:2 [RhCl(cod)]2/P(t-Bu)3 1:2 [RhCl(cod)]2/dtbpbd 1:2 [RhCl(cod)]2/dppp 1:2 [RhCl(cod)]2/BINAP RhCl(PPh3)3 1:2 [RhCl(cod)]2/dppf 1:2 [RhCl(cod)]2/dppf Pd(PPh3)4 Pd(dba)2/P(t-Bu)3 PdCl2(PhCN)2/dppfg NiBr2/dppfg
40 rt 40 40 40 40 40 40 rt 40 40 rt rt rt rt
93 86
