Subscribe to RSS
DOI: 10.1055/a-1608-5693
Bathocuproine-Enabled Nickel-Catalyzed Selective Ullmann Cross-Coupling of Two sp2-Hybridized Organohalides
The National Natural Science Foundation of China (21871211) and the Fundamental Research Funds for the Central Universities (2042019kf0208) supported this work.
Abstract
Cross-coupling reactions are essential for the synthesis of complex organic molecules. Here, we report a nickel-catalyzed Ullmann cross-coupling of two sp2-hybridized organohalides, featuring high cross-selectivity when the two coupling partners are used in a 1:1 ratio. The high chemoselectivity is governed by the bathocuproine ligand. Moreover, the mild reductive reaction conditions allow that a wide range of functional groups are compatible in this Ullmann cross-coupling.
#
Transition-metal-catalyzed cross-coupling reactions have revolutionized the formation of chemical bonds[1] and have played a significant role in medicinal chemistry and materials science.[2] The development of direct dehydrogenative cross-couplings of two nucleophiles[3] and reductive cross-electrophile couplings[4] has not only greatly increased the synthetic scope of cross-coupling reactions, but also conveys the advantages of easy operating conditions and high step economy.[5] Although extraordinary advances have been achieved during the past two decades, chemoselectivity of reactions with two electronically similar coupling partners remains a hot topic in this arena.[6] To obtain cross-selectivity products rather than homo-coupled products, an excess of one coupling partner is usually used, sacrificing the reaction efficiency (Scheme [1]A).[7] Another strategy is installation of a directing group onto one coupling partner (Scheme [1]B),[8] which limits the substrate scope. Additionally, synergistic cooperation[9] of two distinct transition-metal catalysts has been developed to promote reaction efficiency in cross-electrophile coupling reactions (Scheme [1]C).[10] The cross-selectivity of these reactions originates from selective activation of the substrates by different catalysts. Herein we disclose a ligand-enabled, nickel-catalyzed highly cross-selective Ullmann coupling[11] of sp2-hybridized organohalides (Scheme [1]D), which provides an efficient method for the synthesis of both alkenylarenes and diaryl compounds.
Recently, our group reported on nickel-catalyzed migratory cross-electrophile couplings.[12] Experimental evidence indicates that bathocuproine (BC) can promote the transmetallation of two aryl-nickel(II) species (Scheme [2]A),[13] which is the rate-limiting step in nickel-catalyzed homo-couplings of aryl halides.[14] Density functional theory calculations support that the cross-transmetallation of an aryl-nickel(II) species with an alkyl-nickel(II) species is favored over transmetallation of two identical organonickel species. We hypothesized that this theory could be extended to cross-couplings of two different sp2-hybridized organohalides.
From a mechanistic viewpoint, different organohalides exhibit different rates during oxidative addition, which can determine the chemoselectivity of this reaction. However, it remains unclear whether cross-selectivity can also be obtained with two different aryl-nickel(II) species. To exemplify this point, extensive efforts have been devoted to the synthesis of BC-ligated aryl-Ni(II) complexes; however, these were unsuccessful. Next, three electronically diverse, N,N-dimethylpyridine (DMAP)-ligated aryl-Ni(II) complexes (Ni-1, Ni-2, Ni-3) were prepared according to a known method (Scheme [2]B).[15] After obtaining the above Ar-Ni(II) complexes, stoichiometric cross-coupling experiments were conducted (Scheme [2c]). Coupling of a nickel complex bearing an electron-deficient aryl group (Ni-1 or Ni-2) with the nickel complex bearing an electron-rich aryl group (Ni-3) afforded the cross-coupled products 4 or 7 in 64% or 57% yield, respectively, which is more than the combined yield of the two homo-coupled products (29% and 26%, respectively) and the statistical yield (50%). In contrast, the reaction of the two complexes with electronically similar aryl groups (eq. 3) gave rise to the cross-coupled product 8 in 41% yield, which is same proportion as the total yield of the two homo-coupled products (3 and 6, 44% yield) and lower than the statistical yield. These results indicate that cross-selectivity exists in the reactions of two complexes with electronically different aryl groups, but not in the reactions of two complexes with electronically similar aryl groups. This finding clearly demonstrates the possibility of cross-selectivity in the reactions of two nickel complexes, as well as the feasibility of generating cross-coupled diaryl products from a catalytic cycle involving dual Ar-nickel(II) transmetallation.[16]
To prove the feasibility of a nickel-catalyzed cross-coupling of two sp2-hybrided organohalides, we investigated the cross-coupling of 4-bromophenyl 4-methylbenzenesulfonate (9) with 1-bromo-2-methylprop-1-ene (10) as a model reaction (Scheme [3]A). The ligand effect was examined under conditions of 5 mol% NiI2 as the metal catalyst, 1.0 equiv tetrabutylammonium bromide (TBAB) as the additive and dimethylacetamide (DMA) as the solvent. Compared with other common nitrogen-based ligands, BC delivered the optimal result, affording the cross-coupled product 11 in 90% isolated yield.
With the optimal conditions in hand, we turned our attention to investigating the generality of this nickel-catalyzed Ullmann cross-coupling.[17] [18] As shown in Scheme [3]B, a variety of (hetero)aryl bromides and alkenyl bromides with different electronic properties, as well as diverse functional groups and steric environments, were evaluated. Moderate to excellent chemoselectivities were obtained in both aryl-alkenyl (11–20) and aryl-aryl (21–33) cross-coupling reactions with an equal substrate ratio. Notably, when an E,Z-mixed alkyl bromide (E/Z = 3:1) was used, the configuration of the double bond was retained in the products (16–18). Moreover, aryl iodides also reacted efficiently with aryl bromides to give rise to the cross-coupled products in good yields (31–33). However, the aryl chlorides gave poor yield under these reaction conditions due to their low reactivity. It should be noted that poor selectivity was observed in cases with two aryl halides with a large electronic difference. Remarkably, a wide array of functional groups, such as tosylates (11 and 19), tertiary amines (12), ethers (14 and 18), ketones (17 and 29), α,β-unsaturated ketones (20), esters (21, 22, 24, 25, 27 and 33), aldehydes (26), and nitriles (28 and 30), as well as some common heterocycles, including pyridines (12, 24, 25 and 30), benzothiophenes (15), carbazoles (16 and 23), quinolines (26–29), and naphthalenes (21, 25 and 33) were all compatible under these mild nickel-catalyzed reductive reaction conditions. Additionally, a comparable yield (87%) was obtained in a scale-up experiment (10 mmol) of the model reaction (11).
In summary, we have developed a novel nickel-catalyzed Ullmann cross-coupling reaction, providing an efficient method for the synthesis of alkenylarenes and diaryl compounds from widely available aryl halides and/or vinyl halides. The high cross-selectivity is governed by the use of the BC ligand. This protocol has the advantage of an inexpensive catalyst, mild reaction conditions, and extremely good functional group tolerance. Further mechanistic studies are ongoing in our laboratory.
#
Conflict of Interest
The authors declare no conflict of interest.
Supporting Information
- Supporting information for this article is available online at https://doi-org.accesdistant.sorbonne-universite.fr/10.1055/a-1608-5693.
- Supporting Information
-
References and Notes
- 1a Johansson SC. C, Kitching MO, Colacot TJ, Snieckus V. Angew. Chem. Int. Ed. 2012; 51: 5062
- 1b Tortajada A, Julia-Hernandez F, Borjesson M, Moragas T, Martin R. Angew. Chem. Int. Ed. 2018; 57: 15948
- 1c Korch KM, Watson DA. Chem. Rev. 2019; 119: 8192
- 1d Zhang YF, Shi ZJ. Acc. Chem. Res. 2019; 52: 161
- 1e Leitch DC, Becica J. Synlett 2020; 32: 641
- 1f Yuan W, Zheng S, Hu Y. Synthesis 2020; 53: 1719
- 1g Zhao Q, Peng C, Wang Y.-T, Zhan G, Han B. Org. Chem. Front. 2021; 8: 2772
- 2a Busacca CA, Fandrick DR, Song JJ, Senanayake CH. Adv. Syn. Catal. 2011; 353: 1825
- 2b Magano J, Dunetz JR. Chem. Rev. 2011; 111: 2177
- 2c Roughley SD, Jordan AM. J. Med. Chem. 2011; 54: 3451
- 3a Yeung CS, Dong VM. Chem. Rev. 2011; 111: 1215
- 3b Liu C, Yuan J, Gao M, Tang S, Li W, Shi R, Lei A. Chem. Rev. 2015; 115: 12138
- 3c Gao DW, Gu Q, You SL. J. Am. Chem. Soc. 2016; 138: 2544
- 3d Yang Y, Lan J, You J. Chem. Rev. 2017; 117: 8787
- 3e Grzybowski M, Sadowski B, Butenschon H, Gryko DT. Angew. Chem. Int. Ed. 2020; 59: 2998
- 3f Le Z.-G, Zhu Z.-Q, Ji J.-J, Xie Z.-B, Tang J, Yuan E. Synthesis 2020; 53: 2277
- 4a Knappke CE, Grupe S, Gartner D, Corpet M, Gosmini C, Jacobi von Wangelin A. Chem. Eur. J. 2014; 20: 6828
- 4b Gu J, Wang X, Xue W, Gong H. Org. Chem. Front. 2015; 2: 1411
- 4c Wang X, Dai Y, Gong H. Top. Curr. Chem. 2016; 374: 43
- 4d Jarvo ER, Sanford AB. Synlett 2020; 32: 1151
- 4e Rawat VK, Higashida K, Sawamura M. Synthesis 2021; in press; DOI:
- 4f Cong X, Zeng X. Synlett 2021; in press; DOI:
- 7a Amatore M, Gosmini C. Chem. Commun. 2008; 5019
- 7b Krasovskiy A, Duplais C, Lipshutz BH. J. Am. Chem. Soc. 2009; 131: 15592
- 7c Moncomble A, Le Floch P, Lledos A, Gosmini C. J. Org. Chem. 2012; 77: 5056
- 7d Liu J, Ren Q, Zhang X, Gong H. Angew. Chem. Int. Ed. 2016; 55: 15544
- 7e Ding D, Dong H, Wang C. CCS Chem. 2021; 3: 718
- 7f Xu G.-L, Liu C.-Y, Pang X, Liu X.-Y, Shu X.-Z. CCS Chem. 2021; 3: 1147
- 8a Everson DA, Buonomo JA, Weix DJ. Synlett 2014; 25: 233
- 8b Zhang F, Spring DR. Chem. Soc. Rev. 2014; 43: 6906
- 8c Zhang FL, Hong K, Li TJ, Park H, Yu JQ. Science 2016; 351: 252
- 8d Wang Q, Zhang WW, Song H, Wang J, Zheng C, Gu Q, You SL. J. Am. Chem. Soc. 2020; 142: 15678
- 8e Nohira I, Chatani N. ACS Catal. 2021; 11: 4644
- 9a Cong F, Lv XY, Day CS, Martin R. J. Am. Chem. Soc. 2020; 142: 20594
- 9b Kim UB, Jung DJ, Jeon HJ, Rathwell K, Lee SG. Chem. Rev. 2020; 120: 13382
- 9c Sun SZ, Duan Y, Mega RS, Somerville RJ, Martin R. Angew. Chem. Int. Ed. 2020; 59: 4370
- 9d Han X.-W, Zhang T, Yao W.-W, Chen H, Ye M. CCS Chem. 2021; 3: 955
- 9e Jia Y, Liu Y.-Y, Lu L.-Q, Liu S.-H, Zhou H.-B, Lan Y, Xiao W.-J. CCS Chem. 2021; 3: 2032
- 10a Ackerman LK, Lovell MM, Weix DJ. Nature 2015; 524: 454
- 10b Olivares AM, Weix DJ. J. Am. Chem. Soc. 2018; 140: 2446
- 10c Huang L, Ackerman LK. G, Kang K, Parsons AM, Weix DJ. J. Am. Chem. Soc. 2019; 141: 10978
- 10d Kang K, Huang L, Weix DJ. J. Am. Chem. Soc. 2020; 142: 10634
- 11a Dhital RN, Kamonsatikul C, Somsook E, Bobuatong K, Ehara M, Karanjit S, Sakurai H. J. Am. Chem. Soc. 2012; 134: 20250
- 11b Dai L. Prog. Chem. 2018; 30: 1257
- 11c Zuo Z, Kim RS, Watson DA. J. Am. Chem. Soc. 2021; 143: 1328
- 11d Qiu H, Shuai B, Wang YZ, Liu D, Chen YG, Gao PS, Ma HX, Chen S, Mei TS. J. Am. Chem. Soc. 2020; 142: 9872
- 12a Peng L, Li Y, Li Y, Wang W, Pang H, Yin G. ACS Catal. 2017; 8: 310
- 12b Peng L, Li Z, Yin G. Org. Lett. 2018; 20: 1880
- 13 Yin, G.; Peng, L.; Zhao, B.; Li, Y. ChemRxiv
2020, preprint; doi, 10.26434/chemrxiv.12318398.v1. This content is a preprint and has not been peer–reviewed
- 14 Yamamoto T, Wakabayashi S, Osakada K. J. Organomet. Chem. 1992; 428: 223
- 15 Wang X, Ma G, Peng Y, Pitsch CE, Moll BJ, Ly TD, Wang X, Gong H. J. Am. Chem. Soc. 2018; 140: 14490
- 16a Xu H, Diccianni JB, Katigbak J, Hu C, Zhang Y, Diao T. J. Am. Chem. Soc. 2016; 138: 4779
- 16b Yu P, Morandi B. Angew. Chem. Int. Ed. 2017; 56: 15693
- 16c Xiong B, Wang T, Sun H, Li Y, Kramer S, Cheng G.-J, Lian Z. ACS Catal. 2020; 10: 13616
- 17 See the Supporting Information for details.
- 18 The general procedure as well as the analytical data of a few typical compounds are
summarized as follows. Procedure: To an oven-dried 10 mL reaction tube equipped with a magnetic stir bar was introduced,
in an argon-filled glove box, NiI2 (5.0 mol%, 7.8 mg), Bathocuproine (5 mol%, 9.0 mg), n-Bu4NBr (1.0 equiv, 161.2 mg) and zinc dust (1.5 equiv, 49 mg) were added. Then anhydrous
DMA (4 mL) was added and the mixture was stirred, at which time aryl bromide (1 equiv,
0.5 mmol), alkenyl bromide (1 equiv, 0.5 mmol) were added to the resulting mixture
in this order. The tube was sealed with a rubber stopper and stirred at r.t. for 10
h. After the reaction was complete, EtOAc (50 mL) was added and the mixture was extracted
with H2O (20 mL × 3). The combined organic layers were dried over Na2SO4 and concentrated under reduced pressure. The resulting crude product was separated
on a silica gel column with petroleum ether and EtOAc as eluent to afford the desired
product. 4-(2-Methylprop-1-en-1-yl)phenyl 4-methylbenzenesulfonate (11): The reaction was conducted following the general procedure on a 0.5 mmol scale.
The residue was purified by column chromatography on silica gel to afford the product
11 (90% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.72–7.68 (m, 2 H), 7.30–7.28 (m, 2 H), 7.12–7.09 (m, 2 H), 6.92–6.88 (m, 2
H), 6.18 (s, 1 H), 2.43 (s, 3 H), 1.87 (d, J = 1.6 Hz, 3 H), 1.80 (d, J = 1.4 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 147.5, 145.4, 137.7, 136.6, 132.6, 129.83, 129.80, 128.6, 123.9, 122.0, 26.9,
21.8, 19.4. HRMS (ESI): m/z calcd for C17H19O3S ([M + H]+): 303.1049; found: 303.1052.
Corresponding Authors
Publication History
Received: 29 July 2021
Accepted after revision: 24 August 2021
Accepted Manuscript online:
24 August 2021
Article published online:
31 August 2021
© 2021. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References and Notes
- 1a Johansson SC. C, Kitching MO, Colacot TJ, Snieckus V. Angew. Chem. Int. Ed. 2012; 51: 5062
- 1b Tortajada A, Julia-Hernandez F, Borjesson M, Moragas T, Martin R. Angew. Chem. Int. Ed. 2018; 57: 15948
- 1c Korch KM, Watson DA. Chem. Rev. 2019; 119: 8192
- 1d Zhang YF, Shi ZJ. Acc. Chem. Res. 2019; 52: 161
- 1e Leitch DC, Becica J. Synlett 2020; 32: 641
- 1f Yuan W, Zheng S, Hu Y. Synthesis 2020; 53: 1719
- 1g Zhao Q, Peng C, Wang Y.-T, Zhan G, Han B. Org. Chem. Front. 2021; 8: 2772
- 2a Busacca CA, Fandrick DR, Song JJ, Senanayake CH. Adv. Syn. Catal. 2011; 353: 1825
- 2b Magano J, Dunetz JR. Chem. Rev. 2011; 111: 2177
- 2c Roughley SD, Jordan AM. J. Med. Chem. 2011; 54: 3451
- 3a Yeung CS, Dong VM. Chem. Rev. 2011; 111: 1215
- 3b Liu C, Yuan J, Gao M, Tang S, Li W, Shi R, Lei A. Chem. Rev. 2015; 115: 12138
- 3c Gao DW, Gu Q, You SL. J. Am. Chem. Soc. 2016; 138: 2544
- 3d Yang Y, Lan J, You J. Chem. Rev. 2017; 117: 8787
- 3e Grzybowski M, Sadowski B, Butenschon H, Gryko DT. Angew. Chem. Int. Ed. 2020; 59: 2998
- 3f Le Z.-G, Zhu Z.-Q, Ji J.-J, Xie Z.-B, Tang J, Yuan E. Synthesis 2020; 53: 2277
- 4a Knappke CE, Grupe S, Gartner D, Corpet M, Gosmini C, Jacobi von Wangelin A. Chem. Eur. J. 2014; 20: 6828
- 4b Gu J, Wang X, Xue W, Gong H. Org. Chem. Front. 2015; 2: 1411
- 4c Wang X, Dai Y, Gong H. Top. Curr. Chem. 2016; 374: 43
- 4d Jarvo ER, Sanford AB. Synlett 2020; 32: 1151
- 4e Rawat VK, Higashida K, Sawamura M. Synthesis 2021; in press; DOI:
- 4f Cong X, Zeng X. Synlett 2021; in press; DOI:
- 7a Amatore M, Gosmini C. Chem. Commun. 2008; 5019
- 7b Krasovskiy A, Duplais C, Lipshutz BH. J. Am. Chem. Soc. 2009; 131: 15592
- 7c Moncomble A, Le Floch P, Lledos A, Gosmini C. J. Org. Chem. 2012; 77: 5056
- 7d Liu J, Ren Q, Zhang X, Gong H. Angew. Chem. Int. Ed. 2016; 55: 15544
- 7e Ding D, Dong H, Wang C. CCS Chem. 2021; 3: 718
- 7f Xu G.-L, Liu C.-Y, Pang X, Liu X.-Y, Shu X.-Z. CCS Chem. 2021; 3: 1147
- 8a Everson DA, Buonomo JA, Weix DJ. Synlett 2014; 25: 233
- 8b Zhang F, Spring DR. Chem. Soc. Rev. 2014; 43: 6906
- 8c Zhang FL, Hong K, Li TJ, Park H, Yu JQ. Science 2016; 351: 252
- 8d Wang Q, Zhang WW, Song H, Wang J, Zheng C, Gu Q, You SL. J. Am. Chem. Soc. 2020; 142: 15678
- 8e Nohira I, Chatani N. ACS Catal. 2021; 11: 4644
- 9a Cong F, Lv XY, Day CS, Martin R. J. Am. Chem. Soc. 2020; 142: 20594
- 9b Kim UB, Jung DJ, Jeon HJ, Rathwell K, Lee SG. Chem. Rev. 2020; 120: 13382
- 9c Sun SZ, Duan Y, Mega RS, Somerville RJ, Martin R. Angew. Chem. Int. Ed. 2020; 59: 4370
- 9d Han X.-W, Zhang T, Yao W.-W, Chen H, Ye M. CCS Chem. 2021; 3: 955
- 9e Jia Y, Liu Y.-Y, Lu L.-Q, Liu S.-H, Zhou H.-B, Lan Y, Xiao W.-J. CCS Chem. 2021; 3: 2032
- 10a Ackerman LK, Lovell MM, Weix DJ. Nature 2015; 524: 454
- 10b Olivares AM, Weix DJ. J. Am. Chem. Soc. 2018; 140: 2446
- 10c Huang L, Ackerman LK. G, Kang K, Parsons AM, Weix DJ. J. Am. Chem. Soc. 2019; 141: 10978
- 10d Kang K, Huang L, Weix DJ. J. Am. Chem. Soc. 2020; 142: 10634
- 11a Dhital RN, Kamonsatikul C, Somsook E, Bobuatong K, Ehara M, Karanjit S, Sakurai H. J. Am. Chem. Soc. 2012; 134: 20250
- 11b Dai L. Prog. Chem. 2018; 30: 1257
- 11c Zuo Z, Kim RS, Watson DA. J. Am. Chem. Soc. 2021; 143: 1328
- 11d Qiu H, Shuai B, Wang YZ, Liu D, Chen YG, Gao PS, Ma HX, Chen S, Mei TS. J. Am. Chem. Soc. 2020; 142: 9872
- 12a Peng L, Li Y, Li Y, Wang W, Pang H, Yin G. ACS Catal. 2017; 8: 310
- 12b Peng L, Li Z, Yin G. Org. Lett. 2018; 20: 1880
- 13 Yin, G.; Peng, L.; Zhao, B.; Li, Y. ChemRxiv
2020, preprint; doi, 10.26434/chemrxiv.12318398.v1. This content is a preprint and has not been peer–reviewed
- 14 Yamamoto T, Wakabayashi S, Osakada K. J. Organomet. Chem. 1992; 428: 223
- 15 Wang X, Ma G, Peng Y, Pitsch CE, Moll BJ, Ly TD, Wang X, Gong H. J. Am. Chem. Soc. 2018; 140: 14490
- 16a Xu H, Diccianni JB, Katigbak J, Hu C, Zhang Y, Diao T. J. Am. Chem. Soc. 2016; 138: 4779
- 16b Yu P, Morandi B. Angew. Chem. Int. Ed. 2017; 56: 15693
- 16c Xiong B, Wang T, Sun H, Li Y, Kramer S, Cheng G.-J, Lian Z. ACS Catal. 2020; 10: 13616
- 17 See the Supporting Information for details.
- 18 The general procedure as well as the analytical data of a few typical compounds are
summarized as follows. Procedure: To an oven-dried 10 mL reaction tube equipped with a magnetic stir bar was introduced,
in an argon-filled glove box, NiI2 (5.0 mol%, 7.8 mg), Bathocuproine (5 mol%, 9.0 mg), n-Bu4NBr (1.0 equiv, 161.2 mg) and zinc dust (1.5 equiv, 49 mg) were added. Then anhydrous
DMA (4 mL) was added and the mixture was stirred, at which time aryl bromide (1 equiv,
0.5 mmol), alkenyl bromide (1 equiv, 0.5 mmol) were added to the resulting mixture
in this order. The tube was sealed with a rubber stopper and stirred at r.t. for 10
h. After the reaction was complete, EtOAc (50 mL) was added and the mixture was extracted
with H2O (20 mL × 3). The combined organic layers were dried over Na2SO4 and concentrated under reduced pressure. The resulting crude product was separated
on a silica gel column with petroleum ether and EtOAc as eluent to afford the desired
product. 4-(2-Methylprop-1-en-1-yl)phenyl 4-methylbenzenesulfonate (11): The reaction was conducted following the general procedure on a 0.5 mmol scale.
The residue was purified by column chromatography on silica gel to afford the product
11 (90% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.72–7.68 (m, 2 H), 7.30–7.28 (m, 2 H), 7.12–7.09 (m, 2 H), 6.92–6.88 (m, 2
H), 6.18 (s, 1 H), 2.43 (s, 3 H), 1.87 (d, J = 1.6 Hz, 3 H), 1.80 (d, J = 1.4 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 147.5, 145.4, 137.7, 136.6, 132.6, 129.83, 129.80, 128.6, 123.9, 122.0, 26.9,
21.8, 19.4. HRMS (ESI): m/z calcd for C17H19O3S ([M + H]+): 303.1049; found: 303.1052.