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DOI: 10.1055/s-0034-1379205
Generation of Aryl Grignard Reagents from Arene Chromium Tricarbonyl Complexes by Mg(TMP)2·2LiCl and Their Application to Murahashi Coupling
Publication History
Received: 18 August 2014
Accepted: 04 September 2014
Publication Date:
18 September 2014 (online)
Abstract
A mild and straightforward synthesis of biaryls is described that is performed through direct arylation of the C–H bond of (arene)Cr(CO)3 upon deprotonation with Mg(2,2,6,6-tetramethylpiperazide)2·2LiCl and subsequent palladium-catalyzed cross-coupling reaction.
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The biaryl structure is an important motif that is found in many biologically active compounds and organic materials.[1] A reliable synthetic method for the generation of biaryls 1 is transition-metal-catalyzed cross-coupling of aryl–metal reagents Ar–M 2 [2] (M = B(OH)2,[2a] [b] ZnX,[2c] Sn(alkyl)3,[2d] or MgX[2e] [f]) and Ar–X 3 (X = halogen or pseudohalogen, such as OTf or ONf) [Scheme [1], route (i)]; however, these conventional methods have two problems in terms of step economy and functional group compatibility. Thus, regiocontrolled synthesis of aryl halides, which is necessary for the preparation of aryl–metal reagents 2, is not always an easy task. In addition, halogen–metal exchange requires a relatively strong base, such as n-BuLi[3] or i-PrMgCl·LiCl.[4] Oxidative formation of biaryls from unfunctionalized arenes is useful, but presents limited substrate scope.[5] A mild iridium-catalyzed C–H borylation provides facile access to a variety of arylboronic acids but suffers from a lack of regioselectivity.[6] Recent palladium-catalyzed oxidative biaryl formation requires a directing group (e.g., pyridyl, amide, or carboxyl moiety).[7] Knochel et al. have reported a mild C–H arylation of the ortho position relative to electron-withdrawing groups, such as ester, cyanide, and bromide, by directed metalation using a magnesium amide derivative to obtain 6, solving these problems [Scheme [1], route (ii)].[8] On the other hand, the aromatic C–H adjacent to an electron-donating group is deprotonated by lithium amide and (arene)Cr(CO)3, bearing the strongly electron-withdrawing Cr(CO)3 moiety (Scheme [2]).[9] [10] [11] Uemura et al. subjected the resulting arylboromic acid 8,[11] which was generated by deprotonation and transmetalation of 7, to the palladium-catalyzed cross-coupling reaction conditions to generate the corresponding biaryls, albeit in only 10% yield.[12a] This may result from the stabilization of the anion species by the electron withdrawing Cr(CO)3 moiety.[12] Recently, we found that aryl copper species generated from the corresponding Grignard reagents by using Mg(TMP)2·2LiCl were smoothly converted into biaryls in the presence of palladium catalyst.[2g] [13] Herein, we describe a palladium-catalyzed synthesis of biaryls through deprotonation of (arene)Cr(CO)3 using Mg(TMP)2·2LiCl, with subsequent transmetalation to CuI and cross-coupling with an aryl iodide.
We first searched for the optimal amide bases for deprotonation of the (anisole)Cr(CO)3 complex[11c] (7a) and assessed the efficacy by evaluating the D/H ratio after deuteration of the resultant 7a with DCl/D2O (Table [1]). The reaction of 7a and LiTMP[14] gave a complex mixture (entry 1). According to Knochel’s report,[8a] we examined the use of Mg(TMP)2·2LiCl at 0 °C, but found that the starting material 7a was recovered in 85% (entry 2). To promote the deprotonation, we conducted the reaction at room temperature and successfully obtained deuterated (anisole)Cr(CO)3 (11) and 7a in 82% yield as a 66:34 mixture. Disappointingly, however, increased amount of Mg(TMP)2·2LiCl (2.2 equivalents) gave a complex mixture (entry 4). The result indicated that the resultant aryl magnesium species was highly reactive and thus transmetalation to a less reactive metal species would be necessary to achieve a high-yielding process. We employed CuI for transmetalation according to the cross-coupling reaction that was developed in our total synthesis of dictyodendrins[13] (entry 5). Gratifyingly, the addition of CuI prior to elevating the reaction temperature to room temperature resulted in full conversion of 7a to provide deuterated 11 in 80% yield.[15] The successful deprotonation encouraged us to examine other TMP-amide bases. Hauser–Knochel base (TMP)MgCl·LiCl[16] provided a mixture of 11 and 7a (22:78) (entry 6). Unexpectedly, the addition of CuI did not promote the deprotonation (entry 7). On the other hand, Me2Zn(TMP)Li, which was first reported by Uchiyama and co-workers,[17] facilitated smooth deprotonation only in the presence of CuI (entries 8 and 9). The use of (i-Bu)3Al(TMP)Li[18] did not provide any deuterated anisole chromium tricarbonyl complex either in the absence or in the presence of CuI (entries 10 and 11). This optimization study indicated that CuI was essential in promoting the deprotonation of arene chromium tricarbonyl complex.
a The reaction was carried out using 15 mg of (anisole)Cr(CO)3 (7a).
b The ratio was determined by 1H NMR spectroscopic analysis.
c Isolated yield.
d The mixture of 7a and 11 was isolated.
e Not determined.
f The reaction was carried out at 0 °C.
A plausible mechanism is proposed in Scheme [3] to rationalize the unexpected role of CuI in the deprotonation. The starting (arene)Cr(CO)3 7a and aryl magnesium species 12 coexist under equilibrium in the presence of Mg(TMP)2·2LiCl and TMP–H at room temperature, as suggested by the pK a values of TMP–H (ca. 37)[19] and (arene)Cr(CO)3 (<36).[20] No deprotonation was observed when Mg(TMP)2·2LiCl and CuI were premixed, supporting the speculation that Mg(TMP)2·2LiCl acts as a base. The role of CuI is to trap the reactive aryl magnesium species 12 and to promote the deprotonation step by equilibration,[14] giving rise to deuterated anisole 11 on treatment with DCl/D2O.
Next, we focused on the cross-coupling reaction using Mg(TMP)2·2LiCl or Me2Zn(TMP)Li, which was found to act as a superior base in the above preliminary experiments. Complex 7a was successively treated with TMP-amide at 0 °C for 1 h and CuI before reacting with methyl p-iodobenzoate (13a) and Pd(PPh3)4 (Table [2]). Whereas Me2Zn(TMP)Li provided the desired product 9a in 9% yield, (anisole)Cr(CO)3 (7a) was recovered in 78% yield (entry 1). Mg(TMP)2·2LiCl was also effective for the palladium-catalyzed cross-coupling to afford the desired biaryl 9a in 36% yield (entry 2). Next, the amount of Mg(TMP)2·2LiCl and copper iodide was optimized. Reducing the number of equivalents of both Mg(TMP)2·2LiCl and copper iodide to 1.1 equivalents, we obtained biaryl 9a in 54% yield (entry 3). Interestingly, 0.6 equivalents of CuI smoothly converted 7a into biaryl product 9a in 90% yield (entry 4).[21] [22] The use of 0.1 equivalents of CuI substantially reduced the reaction rates and gave trace amounts of biaryl 9a along with 47% of the starting material 7a (entry 5).
a The reaction was performed by using 30 mg of (anisole)Cr(CO)3 (7a).
b Isolated yield.
c The coupling was conducted for 12 h at room temperature.
d The starting material 7a was recovered in 78%.
e The reaction was conducted on a 1 mmol scale using 249 mg of 7a.
f The starting material 7a was recovered in 47%.
Having established the reaction conditions for the synthesis of biaryls, we then investigated the scope and limitations of this synthetic approach (Table [3]). First, we examined aryl iodides bearing a variety of substituents. The coupling reaction of 7a and p-iodoanisole (13b) provided bis-anisole 9b in 48% yield. The formyl group remained intact under the reaction conditions to afford 4-formyl-2′-methoxybiphenyl 9c. The reaction proceeded chemoselectively at the iodo group with p-iodobromobenzene (13d) to provide 9d in excellent yield, leaving the bromine atom untouched. Trifluoromethylphenyl and 3-pyridyl groups were introduced in 53 and 48% yields, respectively. Next, we performed the coupling reaction by using a series of (arene)Cr(CO)3. Fluorobenzene 7b and chlorobenzene derivatives 7c reacted with p-iodobenzoate (13a) at the ortho position of the halogen atom to provide 9g and 9h without formation of benzyne. (3-Fluoroanisole)Cr(CO)3 (7d) and (3-chloroanisole)Cr(CO)3 (7e) were selectively deprotonated at the 2-position to generate 1,2,3-trisubstituted benzene derivatives 9i and 9j in 61 and 40% yields, respectively.
a The reaction was performed by using 0.121 mmol of (arene)Cr(CO)3 7.
b Isolated yield.
c The reaction was conducted by 20 mol% Pd(PPh3)4.
d After successive treatments with Mg(TMP)2·2LiCl at –45 °C and then CuI, the reaction mixture of the substrates was allowed to warm to 0 °C.
According to a recent report by Larrosa, we removed the Cr(CO)3 group by treating 9a with MnO2 to provide biaryl 14 in 66% yield (Scheme [4]).[12d]
In conclusion, we have established mild deprotonation conditions for use with arene chromium tricarbonyl complexes by using a combination of Mg(TMP)2·2LiCl and CuI. The resultant anion species were subjected to the palladium-catalyzed Murahashi cross-coupling reaction to generate the corresponding biaryls in moderate to excellent yields. The broad functional group compatibility of this reaction could constitute a powerful tool for the synthesis of multiply substituted benzene derivatives.
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Acknowledgment
This work was financially supported by the Cabinet Office, Government of Japan through its ‘Funding Program for Next Generation World-Leading Researchers’ (LS008), the JSPS KAKENHI, a Grant-in-Aid for Scientific Research (B) (20390003) and Scientific Research (A) (26253001) for H.T.; Grant-in-Aid for Young Scientists (Start-up; 19890014, B; 21790006 and 23790004), Grant-in-Aid for Scientific Research (C) (25460003), and Grant-in-Aid for Scientific Research on Innovative Areas ‘Molecular Activation Directed toward Straightforward Synthesis’ (25105705) for K.O., Suntory Institute for Bioorganic Research (Sunbor Grant), Astellas Foundation for Research on Metabolic Disorders, Nagase Science and Technology Foundation, and JSPS predoctoral fellowship (for Y.M.).
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References and Notes
- 1a Yamaguchi J, Yamaguchi AD, Itami K. Angew. Chem. Int. Ed. 2012; 51: 8960
- 1b Nicolaou KC, Boddy CN. C, Bräse S, Winssinger N. Angew. Chem. Int. Ed. 1999; 38: 2096
- 1c Wang S, Oldham Jr. WJ, Hudack RA. Jr, Bazan GC. J. Am. Chem. Soc. 2000; 122: 5695
- 2a Suzuki A. Chem. Commun. 2005; 4759
- 2b Saito S, Sakai M, Miyaura N. Tetrahedron Lett. 1996; 37: 2993
- 2c Negishi E. Acc. Chem. Res. 1982; 15: 340
- 2d Stille JK. Angew. Chem., Int. Ed. Engl. 1986; 25: 508
- 2e Tamao K, Sumitani K, Kumada M. J. Am. Chem. Soc. 1972; 94: 4374
- 2f Yamamura M, Moritani I, Murahashi S. J. Organomet. Chem. 1975; 91: C39
- 2g Gooßen LJ, Deng GJ, Levy LM. Science 2006; 313: 662
- 2h Bringmann G, Walter R, Weirich R. Angew. Chem. Int. Ed. Engl. 1990; 29: 977
- 2i Stanforth SP. Tetrahedron 1998; 54: 263
- 2j Hassan J, Sevignon M, Gozzi C, Schulz E, Lemaire M. Chem. Rev. 2002; 102: 1359
- 2k Alberico D, Scott ME, Lautens M. Chem. Rev. 2007; 107: 174
- 2l Martin R, Buchwald SL. Acc. Chem. Res. 2008; 41: 1461
- 3a Rashkin MJ, Hughes RM, Calloway NT, Waters ML. J. Am. Chem. Soc. 2004; 126: 13320
- 3b Liang Y, Fu GC. J. Am. Chem. Soc. 2014; 136: 5520
- 4 Krasovskiy A, Knochel P. Angew. Chem. Int. Ed. 2004; 43: 3333
- 5a Stuart DR, Fagnou K. Science 2007; 316: 1172
- 5b Li R, Jiang L, Lu W. Organometallics 2006; 25: 5973
- 5c Jean A, Cantat J, Bérard D, Bouchu D, Canesi S. Org. Lett. 2007; 9: 2553
- 5d Dwight TA, Rue NR, Charyk D, Josselyn R, DeBoef B. Org. Lett. 2007; 9: 3137
- 5e Dohi T, Ito M, Morimoto K, Iwata M, Kita Y. Angew. Chem. Int. Ed. 2008; 47: 1301
- 5f Ito M, Kubo H, Itani I, Morimoto K, Dohi T, Kita Y. J. Am. Chem. Soc. 2013; 135: 14078
- 5g Campeau L.-C, Fagnou K. Chem. Commun. 2006; 1253
- 5h Campeau L.-C, Stuart DR, Fagnou K. Aldrichimica Acta 2007; 40: 35
- 5i Dohi T, Ito M, Yamaoka N, Morimoto K, Fujioka H, Kita Y. Tetrahedron 2009; 65: 10797
- 5j Dohi T, Kita Y. Chem. Commun. 2009; 2073
- 6a Ishiyama T, Takagi J, Ishida K, Miyaura N, Anastasi NR, Hartwig JF. J. Am. Chem. Soc. 2002; 124: 390
- 6b Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
- 6c Hartwig JF. Acc. Chem. Res. 2012; 45: 864
- 7a Hull KL, Sanford MS. J. Am. Chem. Soc. 2007; 129: 11904
- 7b Wang X, Leow D, Yu J.-Q. J. Am. Chem. Soc. 2011; 133: 13864
- 7c Lyons TW, Sanford MS. Chem. Rev. 2010; 110: 1147
- 7d Neufeldt SR, Sanford MS. Acc. Chem. Res. 2012; 45: 936
- 7e Chen X, Engle KM, Wang DH, Yu J.-Q. Angew. Chem. Int. Ed. 2009; 48: 5094
- 7f Engle KM, Mei T.-S, Wasa M, Yu J.-Q. Acc. Chem. Res. 2012; 45: 788
- 8a Clososki GC, Rohbogner CJ, Knochel P. Angew. Chem. Int. Ed. 2007; 46: 7681
- 8b Rohbogner CJ, Wunderlich SH, Clososki GC, Knochel P. Eur. J. Org. Chem. 2009; 1781
- 8c Haag B, Mosrin M, Ila H, Malakhov V, Knochel P. Angew. Chem. Int. Ed. 2011; 50: 9794
- 9 Prim D, Andrioletti B, Rosa-Munch F, Rose E, Couty F. Tetrahedron 2004; 60: 3325
- 10a Semmelhack MF. Transition Metal Arene Complexes: Nucleophilic Addition In Comprehensive Organometallic Chemistry II . Vol. 12. Wilkinson G, Stone FG. A, Abel EW. Pergamon; New York: 1995: 929-1015
- 10b Pape AR, Kaliappan KP, Kündig EP. Chem. Rev. 2000; 100: 2917
- 11a Semmelhack MF, Bisaha J, Czarny M. J. Am. Chem. Soc. 1979; 101: 768
- 11b Diorazio LJ, Widdowson DA, Clough JM. J. Chem. Soc., Perkin Trans. 1 1992; 421
- 11c Schmalz H.-G, Schelaas K. Angew. Chem., Int. Ed. Engl. 1996; 35: 2146
- 11d Razuvaev GA, Artemov AN, Aladjin AA, Sirotkin NI. J. Organomet. Chem. 1976; 111: 131
- 12a In addition to the boronic acid, Uemura et al. attempted to use the corresponding arylzinc chloride and aryltributyl stannane but obtained no desired biaryl product, see: Uemura M, Nishimura H, Kamikawa K, Nakayama K, Hayashi Y. Tetrahedron Lett. 1994; 35: 1909
- 12b Kamikawa K, Uemura M. Synlett 2000; 938
- 12c Mann IS, Widdowson DA. Tetrahedron 1991; 47: 7981
- 12d Ricci P, Krämer K, Camberio XC, Larrosa I. J. Am. Chem. Soc. 2013; 135: 13258
- 12e McGrew GI, Temaismithi J, Carroll PJ, Walsh PJ. Angew. Chem. Int. Ed. 2010; 49: 5541
- 12f McGrew GI, Stanciu C, Zhang J, Carroll PJ, Dreher SD, Walsh PJ. Angew. Chem. Int. Ed. 2012; 51: 11510
- 13a Okano K, Fujiwara H, Noji T, Fukuyama T, Tokuyama H. Angew. Chem. Int. Ed. 2010; 49: 5925
- 13b Tokuyama H, Okano K, Fujiwara H, Noji T, Fukuyama T. Chem. Asian J. 2011; 6: 560
- 13c Noji T, Fujiwara H, Okano K, Tokuyama H. Org. Lett. 2013; 15: 1946
- 13d Oshiyama T, Satoh T, Okano K, Tokuyama H. RSC Adv. 2012; 2: 5147
- 13e Oshiyama T, Satoh T, Okano K, Tokuyama H. Tetrahedron 2012; 68: 9376
- 13f Noro T, Okano K, Tokuyama H. Synlett 2013; 2143
- 13g Okano K. Yakugaku Zasshi 2013; 133: 1065
- 14 Olofson RA, Dougherty CM. J. Am. Chem. Soc. 1973; 95: 582
- 15 When the reaction was conducted in the presence of CuI at 0 °C, incomplete deprotonation was observed. Premixed Mg(TMP)2·2LiCl and CuI at room temperature for 1 h provided no deuterated anisole 11.
- 16 Krasovskiy A, Krasovskiy V, Knochel P. Angew. Chem. Int. Ed. 2006; 45: 2958
- 17 Uchiyama M, Kobayashi Y, Furuyama T, Nakamura S, Kajihara Y, Miyoshi T, Sakamoto T, Kondo Y, Morokuma K. J. Am. Chem. Soc. 2008; 130: 472
- 18 Naka H, Uchiyama M, Matsumoto Y, Wheatly AE. H, McPartlin M, Morey JV, Kondo Y. J. Am. Chem. Soc. 2007; 129: 1921
- 19a Rathke MW, Kow R. J. Am. Chem. Soc. 1972; 94: 6854
- 19b Olofson RA, Dougherty CM. J. Am. Chem. Soc. 1973; 95: 582
- 20 Brown DA, Raju JR. J. Chem. Soc. A 1966; 40
- 21 The possible active species would be cuprate.
- 22 Synthesis of (Biaryl)Cr(CO)3 9a: A 30 mL two-necked round-bottomed flask equipped with a magnetic stirring bar was charged with 7a (249 mg, 1.02 mmol) and THF (1.0 mL). To the solution was added freshly prepared Mg(TMP)2·2LiCl (0.10 M in THF, 11 mL, 1.1 mmol) dropwise over 5 min at 0 °C. The resulting mixture was stirred at 0 °C for 1 h. To the yellow solution was added CuI (114 mg, 0.60 mmol) portionwise at 0 °C. After the mixture was stirred at 0 °C for 1 h, methyl p-iodobenzoate (13a; 524 mg, 2.0 mmol) and Pd(PPh3)4 (117.9 mg, 102 μmol) were added and the reaction mixture was stirred at r.t. for 1 h. The reaction was quenched with sat. aq NH4Cl, and the mixture was stirred for 10 min. The resulting mixture was filtered through a Celite pad and the filtrate was extracted with Et2O. The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, and filtered. The filtrate was concentrated under reduced pressure to give a crude black solid, which was purified by silica gel column chromatography (EtOAc–hexanes, 1:3 to 1:1) to provide (biaryl)Cr(CO)3 9a (353 mg, 0.915 mmol, 90%) as a dark-red solid. IR (neat): 1955, 1862 (CO stretch), 1715, 1279, 1251, 1111, 825, 773, 662 cm–1; 1H NMR (400 MHz, CDCl3): δ = 8.04 (d, J = 8.0 Hz, 2 H), 7.60 (d, J = 8.0 Hz, 2 H), 5.75 (d, J = 6.8 Hz, 1 H), 5.63 (dd, J = 6.8, 6.8 Hz, 1 H), 5.13 (d, J = 6.8 Hz, 1 H), 4.98 (dd, J = 6.8, 6.8 Hz, 1 H), 3.93 (s, 3 H), 3.76 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ = 232.3, 166.3, 141.1, 138.8, 130.1, 129.7, 129.0, 99.7, 97.7, 94.2, 84.2, 72.9, 55.7, 51.9; MS (EI): m/z = 378 [M]+; HRMS (EI): m/z [M]+ calcd for C18H14CrO6: 378.0196; found: 378.0184.
For a recent report on decarboxylative cross-coupling using benzoic acid derivatives as aryl–metal equivalents to generate aryl–Cu species, see:
For recent reviews, see:
For recent reviews, see:
For recent reviews, see:
For recent reviews, see:
For a review, see:
For recent research on C–H arylation of (arene)Cr(CO)3, see:
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References and Notes
- 1a Yamaguchi J, Yamaguchi AD, Itami K. Angew. Chem. Int. Ed. 2012; 51: 8960
- 1b Nicolaou KC, Boddy CN. C, Bräse S, Winssinger N. Angew. Chem. Int. Ed. 1999; 38: 2096
- 1c Wang S, Oldham Jr. WJ, Hudack RA. Jr, Bazan GC. J. Am. Chem. Soc. 2000; 122: 5695
- 2a Suzuki A. Chem. Commun. 2005; 4759
- 2b Saito S, Sakai M, Miyaura N. Tetrahedron Lett. 1996; 37: 2993
- 2c Negishi E. Acc. Chem. Res. 1982; 15: 340
- 2d Stille JK. Angew. Chem., Int. Ed. Engl. 1986; 25: 508
- 2e Tamao K, Sumitani K, Kumada M. J. Am. Chem. Soc. 1972; 94: 4374
- 2f Yamamura M, Moritani I, Murahashi S. J. Organomet. Chem. 1975; 91: C39
- 2g Gooßen LJ, Deng GJ, Levy LM. Science 2006; 313: 662
- 2h Bringmann G, Walter R, Weirich R. Angew. Chem. Int. Ed. Engl. 1990; 29: 977
- 2i Stanforth SP. Tetrahedron 1998; 54: 263
- 2j Hassan J, Sevignon M, Gozzi C, Schulz E, Lemaire M. Chem. Rev. 2002; 102: 1359
- 2k Alberico D, Scott ME, Lautens M. Chem. Rev. 2007; 107: 174
- 2l Martin R, Buchwald SL. Acc. Chem. Res. 2008; 41: 1461
- 3a Rashkin MJ, Hughes RM, Calloway NT, Waters ML. J. Am. Chem. Soc. 2004; 126: 13320
- 3b Liang Y, Fu GC. J. Am. Chem. Soc. 2014; 136: 5520
- 4 Krasovskiy A, Knochel P. Angew. Chem. Int. Ed. 2004; 43: 3333
- 5a Stuart DR, Fagnou K. Science 2007; 316: 1172
- 5b Li R, Jiang L, Lu W. Organometallics 2006; 25: 5973
- 5c Jean A, Cantat J, Bérard D, Bouchu D, Canesi S. Org. Lett. 2007; 9: 2553
- 5d Dwight TA, Rue NR, Charyk D, Josselyn R, DeBoef B. Org. Lett. 2007; 9: 3137
- 5e Dohi T, Ito M, Morimoto K, Iwata M, Kita Y. Angew. Chem. Int. Ed. 2008; 47: 1301
- 5f Ito M, Kubo H, Itani I, Morimoto K, Dohi T, Kita Y. J. Am. Chem. Soc. 2013; 135: 14078
- 5g Campeau L.-C, Fagnou K. Chem. Commun. 2006; 1253
- 5h Campeau L.-C, Stuart DR, Fagnou K. Aldrichimica Acta 2007; 40: 35
- 5i Dohi T, Ito M, Yamaoka N, Morimoto K, Fujioka H, Kita Y. Tetrahedron 2009; 65: 10797
- 5j Dohi T, Kita Y. Chem. Commun. 2009; 2073
- 6a Ishiyama T, Takagi J, Ishida K, Miyaura N, Anastasi NR, Hartwig JF. J. Am. Chem. Soc. 2002; 124: 390
- 6b Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
- 6c Hartwig JF. Acc. Chem. Res. 2012; 45: 864
- 7a Hull KL, Sanford MS. J. Am. Chem. Soc. 2007; 129: 11904
- 7b Wang X, Leow D, Yu J.-Q. J. Am. Chem. Soc. 2011; 133: 13864
- 7c Lyons TW, Sanford MS. Chem. Rev. 2010; 110: 1147
- 7d Neufeldt SR, Sanford MS. Acc. Chem. Res. 2012; 45: 936
- 7e Chen X, Engle KM, Wang DH, Yu J.-Q. Angew. Chem. Int. Ed. 2009; 48: 5094
- 7f Engle KM, Mei T.-S, Wasa M, Yu J.-Q. Acc. Chem. Res. 2012; 45: 788
- 8a Clososki GC, Rohbogner CJ, Knochel P. Angew. Chem. Int. Ed. 2007; 46: 7681
- 8b Rohbogner CJ, Wunderlich SH, Clososki GC, Knochel P. Eur. J. Org. Chem. 2009; 1781
- 8c Haag B, Mosrin M, Ila H, Malakhov V, Knochel P. Angew. Chem. Int. Ed. 2011; 50: 9794
- 9 Prim D, Andrioletti B, Rosa-Munch F, Rose E, Couty F. Tetrahedron 2004; 60: 3325
- 10a Semmelhack MF. Transition Metal Arene Complexes: Nucleophilic Addition In Comprehensive Organometallic Chemistry II . Vol. 12. Wilkinson G, Stone FG. A, Abel EW. Pergamon; New York: 1995: 929-1015
- 10b Pape AR, Kaliappan KP, Kündig EP. Chem. Rev. 2000; 100: 2917
- 11a Semmelhack MF, Bisaha J, Czarny M. J. Am. Chem. Soc. 1979; 101: 768
- 11b Diorazio LJ, Widdowson DA, Clough JM. J. Chem. Soc., Perkin Trans. 1 1992; 421
- 11c Schmalz H.-G, Schelaas K. Angew. Chem., Int. Ed. Engl. 1996; 35: 2146
- 11d Razuvaev GA, Artemov AN, Aladjin AA, Sirotkin NI. J. Organomet. Chem. 1976; 111: 131
- 12a In addition to the boronic acid, Uemura et al. attempted to use the corresponding arylzinc chloride and aryltributyl stannane but obtained no desired biaryl product, see: Uemura M, Nishimura H, Kamikawa K, Nakayama K, Hayashi Y. Tetrahedron Lett. 1994; 35: 1909
- 12b Kamikawa K, Uemura M. Synlett 2000; 938
- 12c Mann IS, Widdowson DA. Tetrahedron 1991; 47: 7981
- 12d Ricci P, Krämer K, Camberio XC, Larrosa I. J. Am. Chem. Soc. 2013; 135: 13258
- 12e McGrew GI, Temaismithi J, Carroll PJ, Walsh PJ. Angew. Chem. Int. Ed. 2010; 49: 5541
- 12f McGrew GI, Stanciu C, Zhang J, Carroll PJ, Dreher SD, Walsh PJ. Angew. Chem. Int. Ed. 2012; 51: 11510
- 13a Okano K, Fujiwara H, Noji T, Fukuyama T, Tokuyama H. Angew. Chem. Int. Ed. 2010; 49: 5925
- 13b Tokuyama H, Okano K, Fujiwara H, Noji T, Fukuyama T. Chem. Asian J. 2011; 6: 560
- 13c Noji T, Fujiwara H, Okano K, Tokuyama H. Org. Lett. 2013; 15: 1946
- 13d Oshiyama T, Satoh T, Okano K, Tokuyama H. RSC Adv. 2012; 2: 5147
- 13e Oshiyama T, Satoh T, Okano K, Tokuyama H. Tetrahedron 2012; 68: 9376
- 13f Noro T, Okano K, Tokuyama H. Synlett 2013; 2143
- 13g Okano K. Yakugaku Zasshi 2013; 133: 1065
- 14 Olofson RA, Dougherty CM. J. Am. Chem. Soc. 1973; 95: 582
- 15 When the reaction was conducted in the presence of CuI at 0 °C, incomplete deprotonation was observed. Premixed Mg(TMP)2·2LiCl and CuI at room temperature for 1 h provided no deuterated anisole 11.
- 16 Krasovskiy A, Krasovskiy V, Knochel P. Angew. Chem. Int. Ed. 2006; 45: 2958
- 17 Uchiyama M, Kobayashi Y, Furuyama T, Nakamura S, Kajihara Y, Miyoshi T, Sakamoto T, Kondo Y, Morokuma K. J. Am. Chem. Soc. 2008; 130: 472
- 18 Naka H, Uchiyama M, Matsumoto Y, Wheatly AE. H, McPartlin M, Morey JV, Kondo Y. J. Am. Chem. Soc. 2007; 129: 1921
- 19a Rathke MW, Kow R. J. Am. Chem. Soc. 1972; 94: 6854
- 19b Olofson RA, Dougherty CM. J. Am. Chem. Soc. 1973; 95: 582
- 20 Brown DA, Raju JR. J. Chem. Soc. A 1966; 40
- 21 The possible active species would be cuprate.
- 22 Synthesis of (Biaryl)Cr(CO)3 9a: A 30 mL two-necked round-bottomed flask equipped with a magnetic stirring bar was charged with 7a (249 mg, 1.02 mmol) and THF (1.0 mL). To the solution was added freshly prepared Mg(TMP)2·2LiCl (0.10 M in THF, 11 mL, 1.1 mmol) dropwise over 5 min at 0 °C. The resulting mixture was stirred at 0 °C for 1 h. To the yellow solution was added CuI (114 mg, 0.60 mmol) portionwise at 0 °C. After the mixture was stirred at 0 °C for 1 h, methyl p-iodobenzoate (13a; 524 mg, 2.0 mmol) and Pd(PPh3)4 (117.9 mg, 102 μmol) were added and the reaction mixture was stirred at r.t. for 1 h. The reaction was quenched with sat. aq NH4Cl, and the mixture was stirred for 10 min. The resulting mixture was filtered through a Celite pad and the filtrate was extracted with Et2O. The combined organic extracts were washed with brine, dried over anhydrous Na2SO4, and filtered. The filtrate was concentrated under reduced pressure to give a crude black solid, which was purified by silica gel column chromatography (EtOAc–hexanes, 1:3 to 1:1) to provide (biaryl)Cr(CO)3 9a (353 mg, 0.915 mmol, 90%) as a dark-red solid. IR (neat): 1955, 1862 (CO stretch), 1715, 1279, 1251, 1111, 825, 773, 662 cm–1; 1H NMR (400 MHz, CDCl3): δ = 8.04 (d, J = 8.0 Hz, 2 H), 7.60 (d, J = 8.0 Hz, 2 H), 5.75 (d, J = 6.8 Hz, 1 H), 5.63 (dd, J = 6.8, 6.8 Hz, 1 H), 5.13 (d, J = 6.8 Hz, 1 H), 4.98 (dd, J = 6.8, 6.8 Hz, 1 H), 3.93 (s, 3 H), 3.76 (s, 3 H); 13C NMR (100 MHz, CDCl3): δ = 232.3, 166.3, 141.1, 138.8, 130.1, 129.7, 129.0, 99.7, 97.7, 94.2, 84.2, 72.9, 55.7, 51.9; MS (EI): m/z = 378 [M]+; HRMS (EI): m/z [M]+ calcd for C18H14CrO6: 378.0196; found: 378.0184.
For a recent report on decarboxylative cross-coupling using benzoic acid derivatives as aryl–metal equivalents to generate aryl–Cu species, see:
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For recent research on C–H arylation of (arene)Cr(CO)3, see:
