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DOI: 10.1055/a-2081-8907
Borylative Difunctionalization of Unsaturated Hydrocarbons Using Borylcopper Species
Abstract
This account summarizes the Cu-catalyzed borylative functionalizations of unsaturated hydrocarbons that we have developed over the past decade. First, we focus on the regioselective hydroboration of unsymmetrical internal alkynes and 1,2-dienes. Secondly, a borylative allyl–allyl coupling using 1,2-dienes, B2pin2, and an allyl phosphate is presented. Thirdly, we introduce the boroacylation and boroformylation of 1,2-dienes by using an acid anhydride or formate, respectively, as the electrophile. Lastly, we describe the synthesis of 2-boryl-1,3-butadienes and cyclic allylborates. These reactions offer a versatile method for synthesizing a broad range of useful compounds and also provide a detailed understanding of the reaction mechanism, which could lead to the development of catalysts that are both more efficient and more selective.
1 Introduction
2 Hydroboration of Alkynes
3 Hydroboration of 1,2-Dienes and 1,3-Dienes
4 Synthesis of 2-Boryl-1,3-butadienes
5 Boroallylation of 1,2-Dienes
6 Boroacylation of 1,2-Dienes
7 Boroformylation of 1,2-Dienes and 1,3-Dienes
8 Synthesis of Cyclic Allylborates
9 Conclusion and Outlook
#
Biographical Sketch
Tetsuaki Fujihara was born in Japan in 1973. He received his Bachelor of Science degree from Shizuoka University in 1996 and his Ph.D. degree in 2001 from Hokkaido University under the supervision of Professors Yoichi Sasaki and Taira Imamura. Subsequently, he conducted postdoctoral research with Professor Koji Tanaka at Institute for Molecular Science. In 2004, he joined Professor Yasushi Tsuji’s group at the Catalysis Research Center, Hokkaido University, as a postdoctoral fellow. He was appointed as an assistant professor at Kyoto University in 2006, and in 2017, he was promoted to associate professor, and to full professor in 2022. He received the Thieme Chemistry Journal Award in 2015. His research interests are related to the development of transition-metal-catalyzed organic transformations, including the utilization of carbon dioxide in organic synthesis.
Introduction
Organoboronic acids and their esters[1] can be commonly used in several carbon–oxygen, carbon–nitrogen, and carbon–carbon bond-forming reactions, such as the Chan–Lam coupling reaction[2] and the Suzuki–Miyaura cross-coupling reaction.[3] Therefore, developing simple and effective methods for preparing a wide variety of organoboron compounds is of great importance. Classically, the hydroboration of unsaturated hydrocarbons[4] or the reactions of Grignard or organolithium reagents with boron electrophiles[1] are well-established synthetic methods; however, difficulties in controlling the selectivity and a limited functional-group tolerance are among the disadvantages of these methods.
Borylation reactions using transition-metal catalysts and bis(pinacolato)diboron (B2pin2)[5] have emerged as effective synthetic methods. For example, the Pd-catalyzed borylation of organic halides with B2pin2,[6] and the Ir-catalyzed borylation of carbon–hydrogen bonds with B2pin2 [7] have been reported to date. These methods can provide a wide variety of organoboron compounds; however, precious metals must be used in these transformations.
Cu-catalyzed borylative transformations are also efficient methods for preparing functionalized organoboron compounds.[8] The reactions basically proceed under mild reaction conditions. One of the key steps in borylative transformation is the generation of boryl copper intermediates. Sadighi and co-workers first reported the synthesis and characterization of a borylcopper complex bearing 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr), an N-heterocyclic carbene (NHC), as the ligand (Scheme [1]).[9] We also isolated a borylcopper complex bearing 4,5-dichloro-1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (ClIPr) as the ligand in a moderate yield.[10]
This account summarizes several borylative difunctionalizations of unsaturated hydrocarbons using borylcopper compounds as active species. The account includes the following transformations: (1) regioselective hydroborations of unsymmetrical internal alkynes and 1,2-dienes; (2) borylative allyl–allyl couplings (boroallylation of 1,2-dienes); (3) boroacylation and boroformylation of 1,2-dienes using an acid anhydride and a formate, respectively; (4) the synthesis of 2-boryl-1,3-butadienes and cyclic allylborates. These reactions have several potential benefits for the synthetic community. First, they offer versatile methods for the syntheses of a broad range of useful compounds. Secondly, they provide a detailed understanding of the reaction mechanism, which could lead to the development of catalysts that are both more efficient and more selective.
# 2
Hydroboration of Alkynes
The hydroboration of alkynes is of importance because alkenyl boranes are indispensable starting materials in organic transformations such as the Suzuki–Miyaura cross-coupling reaction.[3] The hydroboration of terminal alkynes is known to proceed regio- and stereoselectively.[11] In contrast, the hydroboration of unsymmetrical internal alkynes is challenging because of the difficulty in controlling the regioselectivity.
Before we started our project, Kim and Yun reported a regioselective hydroboration of unsymmetrical internal alkynes using a CuCl/P(p-Tol)3 catalyst system in THF (Equation 1).[12]
On the basis of this background, we focused on the ligand- and reagent-controlled regioselective hydroboration using Cu catalysts and we developed a regioselective hydroboration of unsymmetrical internal alkynes (Scheme [2]).[13] The reaction was carried out using B2pin2 and methanol as a boron source and a proton source, respectively, in the presence of CuCl and CF3Ar-Xan, a Xantphos derivative with 3,5-bis(trifluoromethyl)phenyl groups on the phosphorus atoms, as the ligand in toluene under mild reaction conditions. The reaction was applicable to a wide range of unsymmetrical internal alkynes, including those with secondary alkyl moieties attached to the sp carbon. Alkynes bearing conjugated ester or amide functionalities also afforded the corresponding β-products in high yields and with a high regioselectivity.
A plausible reaction mechanism is shown in Scheme [3]. An alkoxy copper species reacts with B2pin2 to generate a borylcopper species, as shown in Scheme [1] (step 1).[9] [10] The addition of the borylcopper to the C≡C triple bond affords an alkenylcopper intermediate (step 2); this is the regiodetermining step. Next, protonation with the alcohol provides a hydroborated product, and the alkoxy copper is regenerated (step 3).
As described above, the hydroboration of unsymmetrical internal alkynes proceeded β-selectively through the addition of borylcopper species across the alkynes. Meanwhile, copper hydride species can be utilized for the hydroboration of alkynes.[14] When B2pin2 was replaced with pinacolborane (HBpin), with MeAr-Xan (a Xantphos derivative with 3,5-xylyl groups on the phosphorus atoms) as a ligand, the regioselectivity was reversed to afford the α-borylated products selectively (Scheme [4]).[13]
As shown in Scheme [2] and Scheme [4], the regioselectivity of the hydroboration was switched (Scheme [5]).[13] Both the copper hydride and borylcopper species add across the unsymmetrical internal alkyne regioselectively with the aid of an aryl, ester, or amide moiety. As a result, a reagent-controlled hydroboration was achieved.
# 3
Hydroboration of 1,2-Dienes and 1,3-Dienes
We next turned our attention to the use of 1,2-dienes as substrates for the hydroboration reactions, because controlling the regio- and stereoselectivity is a highly challenging task. Regarding this issue, the groups of Hoveyda and Ma have independently reported hydroborations of 1,2-dienes.[15] [16]
Employing monosubstituted 1,2-dienes as substrates with ClIPrCuCl as a catalyst and MeOH as a proton source afforded the corresponding alkenylboronates having an exo-methylene moiety (Scheme [6], Conditions A).[10] In contrast, (Z)-internal alkenylboronates were obtained by using a Cu complex with MeIMes as the ligand and an excess amount of methanol in toluene at low temperature (Scheme [6], Conditions B).
To obtain insights into the borylcupration step, a stoichiometric reaction between a borylcopper complex bearing ClIPr as the ligand and 1-phenylpropadiene was carried out (Equation 2).[10] A (Z)-σ-allylcopper complex was regioselectively obtained, and its structure was determined by X-ray crystallographic analysis.
Scheme [7] shows a possible catalytic cycle for the hydroboration to afford vinylboranes based on the stoichiometric reactions. A borylcopper species inserts into the 1,2-diene from its sterically less-hindered side to give a (Z)-σ-allylcopper intermediate (Scheme [7], step 1). By employing a bulky NHC ligand such as ClIPr, the allyl copper is protonated to afford an alkenyl boronates with an exo-methylene moiety (step 2). In contrast, the allylcopper species can be protonated in the case of less-bulky MeIMes as the ligand, giving an internal alkenyl boronate (step 4). Finally, σ-bond metathesis between the alkoxy copper and B2pin2 regenerates the borylcopper species (step 3 or 5).
We next surmised that analogous catalytic systems might be applicable to the hydroboration of 1,3-dienes (Scheme [8]).[10] When 1-phenyl-1,3-butadiene was used as the substrate, a 3,4-hydroborated product was isolated in high yield with high selectivity by employing ClAr-Xan, a Xantphos derivative with 3,5-dichlorophenyl groups, as a ligand in toluene. In contrast, the reaction using IMesCuCl as a catalyst and t-BuOH as a proton source in THF afforded a 1,4-hydroborated (Z)-allylboranate with highly selectively.
# 4
Synthesis of 2-Boryl-1,3-butadienes
During our work on the regioselective hydroboration of 1,2-dienes described above, we found that the installation of a leaving group at a suitable position of the substrate can result in a new unsaturated bond after elimination.[17] We therefore used 1,2-dienes containing alkoxy groups as substrates for Cu-catalyzed borylation (Scheme [9]).[18] By employing the Cu complex bearing a bulky NHC ligand as the catalyst and α-alkoxyallenes as substrates, we obtained 2-boryl-1,3-butadienes.
A possible reaction mechanism is shown in Scheme [10]. The borylcopper species adds across an internal carbon–carbon bond in the 1,2-diene to afford a σ-allylcopper intermediate (Scheme [10], step 1). Elimination of the benzyloxy moiety occurs, and a 2-boryl-1,3-butadiene and a copper alkoxide (LCuOBn) are generated (step 2). Finally, a borylcopper species is formed by the reaction of LCuOBn with B2pin2 (step 3), and the catalytic cycle is closed.
# 5
Boroallylation of 1,2-Dienes
The organocopper species formed by the addition of borylcopper species to unsaturated hydrocarbons can act as nucleophiles. Cu-catalyzed carboborations of alkynes have been reported independently by the groups of Tortosa[19] and Yoshida.[20] We surmised that β-borylallyl copper species of the type shown in Equation 2 might be captured by carbon electrophiles, especially, allyl electrophiles. Allyl–allyl coupling reactions of allyl nucleophiles with allyl electrophiles should then produce 1,5-dienes, but controlling the regio- and stereoselectivity would be a challenging task.
We developed the boroallylation of 1,2-dienes by using an allylic phosphate as an electrophile (Scheme [11]).[21] A copper catalyst with the cyclohexyl-substituted NHC ligand ICy was found to be effective for the transformation. Several 1,2-dienes and allylic phosphates were converted into 2-boryl-1,5-diene derivatives with high regioselectivities.
A possible catalytic cycle is shown in Scheme [12]. An alkoxy copper species reacts with B2pin2 to afford a borylcopper species (Scheme [12], step 1). The1,2-diene then reacts with the borylcopper to produce a β-boryl (Z)-σ-allyl copper species, as shown in Equation 2 (step 2). Next, the addition of the allylcopper to the C=C bond of the allylic phosphate gives an alkylcopper intermediate (step 3). Subsequently, β-elimination with release of a copper phosphate provides the product (step 4). Finally, the reaction of the copper phosphate with t-BuOK regenerates the alkoxy copper species (step 5).
Hoveyda and co-workers reported an asymmetric boroallylation of 1.2-dienes using copper catalysts with a chiral NHC ligand (Equation 3).[22] This reaction proceeded regio- and stereoselectively.
Yoshida also developed a reaction of 1,2-dienes, B2pin2, and benzyl chloride, by applying their knowledge of the reaction of alkenes to that of 1,2-dienes (Equation 4).[23] By employing 1,1′-bis(diphenylphosphino)ferrocene (dppf) as a ligand, the reaction using the unsymmetrical diboron reagent pinB–Bdan afforded the desired product.
# 6
Boroacylation of 1,2-Dienes and 1,3-Dienes
Carbonyl compounds with a boron moiety are good platforms because these functional groups are often used to form new carbon–carbon bonds by established methods. The group of Gagosz and Riant found that the boroacylation of 1,2-dienes proceeded using an acyl fluoride as the electrophile (Equation 5).[24] The reactions proceed with a Cu(OAc)2/dppf catalyst system and sodium trimethylsilanoate (TMSONa). Later, Zhang and co-workers reported an enantioselective boroacylation of 1,2-dienes using a chiral ligand.[25]
We also reported boroacylation of 1,2-dienes (Scheme [13]).[26] Reactions of 1,2-dienes, B2pin2, and acid anhydrides were carried out in the presence of a catalytic amount of CuOAc and the bulky bidentate phosphine DTBM-dppbz as a ligand, with potassium 2,4,6-trimethylbenzoate (MesCO2K) as an additive. The reaction proceeded from a wide range of substrates, and β-boryl β,γ-unsaturated ketones were obtained regioselectively.
Brown and co-workers reported a boroacylation of 1,3-dienes as one of the substrates for reactions using alkenes.[27] The reaction of 1-phenyl-1,3-butadiene, B2pin2, and pivaloyl chloride proceeded with SIMesCuCl [SIMes = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene] as a catalyst at room temperature. Mixtures of 4,3- and 4,1-boroacylated products were obtained in good yields and with moderate selectivity (Equation 6).
# 7
Boroformylation of 1,2-Dienes and 1,3-Dienes
On the basis of the results of the boroacylations described above, we next used formate esters as electrophiles to synthesize aldehydes (Scheme [14]).[28] The reactions of 1,2-dienes, B2pin2, and hexyl formate were carried out using a CuOAc/DTBM-dppbz catalyst system to give β-boryl-β,γ-unsaturated aldehydes in good to high isolated yields. In the case of 1,2-dienes with functionalities such as 4-chlorophenyl, ester, or carbamate groups, sodium laurate was found to be an efficient additive.
Scheme [15] shows a plausible catalytic cycle for the boroformylation. The borylcopper species adds across the terminal double bond of the 1,2-diene, giving a β-boryl-allylcopper intermediate (Scheme [15], step 1). This then reacts with a formate to afford an alkoxylated intermediate via a six-membered ring transition state (step 2). Next, β-elimination produces the desired product and an alkoxycopper species (step 3). Finally, the reaction of the alkoxycopper species with B2pin2 regenerates the active borylcopper species (step 4).
We next turned our attention to the use of 1,3-dienes as substrates in boroformylation (Scheme [16]).[29] The reactions using 2,3-disubstituted 1,3-butadienes was carried out at room temperature in toluene using a monodentate phosphine, P(3,5-Ph2C6H3)3, as the ligand. As a result, 1,2-boroformylated products were obtained in excellent yields with perfect regioselectivity. The reaction of 2-phenyl-1,3-butadiene proceeded regioselectively to afford the 1,2-boroformylated product in a moderate yield.
# 8
Synthesis of Cyclic Allylborates
As described above, regioselective boroformylation was achieved. In order to clarify the regiodetermining step, a stoichiometric reaction was carried out (Equation 7).[30] The reaction of 2,3-diphenyl-1,3-butadiene, IPrCuOtBu, and B2pin2 was conducted in THF at room temperature. After recrystallization of the reaction mixture, we found that a Cu complex having a cyclic allylborate was formed, and its structure was confirmed by X-ray crystallographic analysis. The Cu had a linear geometry with a C(NHC)–Cu–O bond angle of 179.1(1)°. The boron center had a distorted tetrahedral geometry, owing to the coordination to Cu.
Next, we tested the catalytic synthesis of cyclic allylborates. With IPrCuCl as a catalyst, the reaction of 2,3-dimethyl-1,3-diene (1, R1 = R2 = Me), B2pin2, and t-BuOLi as a base proceeded smoothly at room temperature (Scheme [17]) to give the cyclic allylborate 2 (R1 = R2 = Me) in 98% isolated yield. Under these reaction conditions, various 2,3-disubstituted-1,3-dienes 1 were converted into the corresponding cyclic allylborates 2.
Based on the stoichiometric reactions shown in Equation 7, a plausible reaction mechanism was proposed, as shown in Scheme [18]. Copper alkoxide A reacts with B2pin2 to produce a borylcopper complex B (Scheme [18], step 1). This adds to the 1,3-diene to form the allylcopper intermediate C (step 2). Next, the intramolecular nucleophilic attack of the allylcopper at an electrophilic boron center generates intermediate D, which was characterized by X-ray crystallography (equation 7). Finally, the cyclic allylborate is formed by cation exchange between the copper species D and the alkoxide (step 4).
# 9
Conclusions and Future Outlook
In this Account, we have summarized the Cu-catalyzed borylative difunctionalization of unsaturated hydrocarbons, including the regioselective hydroboration of unsymmetrical internal alkynes and 1,2-dienes, the boroallylation of 1,2-dienes, the boroacylation of 1,2-dienes, the boroformylation of 1,2-dienes, and the syntheses of 2-boryl-1,3-butadienes and cyclic allylborates. One of the key steps in these transformations is the regioselective generation of an organocopper species obtained by the reaction of borylcopper species with unsaturated hydrocarbons. By controlling the reaction with electrophiles, the desired products can be obtained in high yields with high selectivity.
Our research has demonstrated an approach for designing ligands that has resulted in high product yields and selectivities; however, ligand effects strongly depend on various factors such as the nature of the reaction and/or the types of substrates. Our group aims to contribute to organic synthesis by developing highly active and highly selective catalytic reactions that can advance this field from this perspective. We hope that the insights gained from our research will inspire the development of new catalytic reactions for the functionalization of unsaturated hydrocarbons.
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Conflict of Interest
The authors declare no conflict of interest.
Acknowledgment
The author is deeply grateful to Professor Emeritus Yasushi Tsuji for his helpful advice and encouragement throughout all research works that the author has summarized in this Account.
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For Pd-catalyzed borylations, see:
For Ir-catalyzed borylations, see:
For Cu-catalyzed borylations, see:
For selected examples, see:
For selected examples, see:
Corresponding Author
Publication History
Received: 11 April 2023
Accepted after revision: 26 April 2023
Accepted Manuscript online:
26 April 2023
Article published online:
05 June 2023
© 2023. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
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References
- 1 Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials, 2nd ed. Hall DG. Wiley-VCH; Weinheim: 2011
- 2a West MJ, Fyfe JW. B, Vantourout JC, Watson AJ. B. Chem. Rev. 2019; 119: 12491
- 2b Chen J.-Q, Li J.-H, Dong Z.-B. Adv. Synth. Catal. 2020; 362: 3311
- 3a Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
- 3b Hayashi T, Yamasaki K. Chem. Rev. 2003; 103: 2829
- 3c Miyaura N. Bull. Chem. Soc. Jpn. 2008; 81: 1535
- 4a Brown HC. Pure Appl. Chem. 1976; 47: 49
- 4b Beletskaya L, Pelter A. Tetrahedron 1997; 53: 4957
- 4c Crudden CM, Edwards D. Eur. J. Org. Chem. 2003; 4695
- 4d Carroll A.-M, O’Sullivan TP, Guiry PJ. Adv. Synth. Catal. 2005; 347: 609
- 5 Neeve EC, Geier SJ, Mkhalid IA. I, Westcott SA, Marder TB. Chem. Rev. 2016; 116: 9091
- 6a Rout L, Punniyamurthy T. Coord. Chem. Rev. 2021; 431: 213675
- 6b Chow WK, Yuen OY, Choy PY, So CM, Lau CP, Wong WT, Kwong FY. RSC Adv. 2013; 3: 12518
- 7a Su B, Hartwig JF. Angew. Chem. Int. Ed. 2022; 61: e202113343
- 7b Veth L, Grab HA, Dydio P. Synthesis 2022; 54: 3482
- 7c Li Y, Wu X.-F. Angew. Chem. Int. Ed. 2020; 59: 1770
- 7d Wright JS, Scott PJ. H, Steel PG. Angew. Chem. Int. Ed. 2021; 60: 2796
- 7e Kuroda Y, Nakao Y. Chem. Lett. 2019; 48: 1092
- 7f Hartwig JF. Acc. Chem. Res. 2012; 45: 864
- 7g Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
- 7h Ishiyama T, Miyaura N. Pure Appl. Chem. 2006; 78: 1369
- 8a Alam S, Karim R, Khan A, Pal AK. A. K, Maruani A. Eur. J. Org. Chem. 2021; 6115
- 8b Perry GJ. P, Jia T, Procter DJ. ACS Catal. 2020; 10: 1485
- 8c Fujihara T, Tsuji Y. Synthesis 2018; 50: 1737
- 8d Tsuji Y, Fujihara T. Chem. Rec. 2016; 16: 2294
- 8e Yoshida H. Chem. Rec. 2016; 16: 419
- 8f Yoshida H. ACS Catal. 2016; 6: 1799
- 8g Semba Y, Fujihara T, Terao J, Tsuji Y. Tetrahedron 2015; 71: 2183
- 8h Yun J. Asian J. Org. Chem. 2013; 1016
- 9a Laitar DS, Müller P, Sadighi JP. J. Am. Chem. Soc. 2005; 127: 17196
- 9b Zhao H, Lin Z, Marder TB. J. Am. Chem. Soc. 2006; 128: 15637
- 10 Semba K, Shinomiya M, Fujihara T, Terao J, Tsuji Y. Chem. Eur. J. 2013; 19: 7125
- 11a Pereira S, Srebnik M. Organometallics 1995; 14: 3127
- 11b Ohmura T, Yamamoto Y, Miyaura N. J. Am. Chem. Soc. 2000; 122: 4990
- 11c Wang YD, Kimball G, Prashad AS, Wang Y. Tetrahedron Lett. 2005; 46: 8777
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For Pd-catalyzed borylations, see:
For Ir-catalyzed borylations, see:
For Cu-catalyzed borylations, see:
For selected examples, see:
For selected examples, see: