Tertiary Alkylative Suzuki–Miyaura Couplings

Abstract

Suzuki–Miyaura coupling is an extremely useful way to construct Csp²–Csp² carbon bonds. On the other hand, Csp²–Csp³ coupling reactions do not work well, and tert-alkylative Suzuki–Miyaura coupling is particularly challenging due to problematic oxidative addition and β-hydride elimination side reactions. In this short review, we will introduce recent examples of tert-alkylative Suzuki–Miyaura couplings with tert-alkyl electrophiles or -boron reagents. The review will mainly focus on catalyst and product structures and on the proposed mechanisms.

1 Introduction

2 Ni-Catalyzed tert-Alkylative Couplings

3 Pd-Catalyzed tert-Alkylative Couplings

4 Fe-Catalyzed tert-Alkylative Couplings

5 tert-Alkylative Couplings with 1-Alkenyl Borons

6 tert-Alkylative Couplings under Photoirradiation

7 Stereospecific tert-Alkylative Couplings

8 Conclusion

Introduction

The Suzuki–Miyaura (S-M) coupling is one of the most powerful technologies available for the construction of π-conjugated compounds.[1] Although the S-M coupling is the best choice to construct C_sp2–C_sp2 bonds and many applications can be seen in the literature, alkyl couplings, especially those involving a tertiary alkyl group, are particularly challenging to achieve. We can understand the difficulty in coupling a tert-alkyl group in an S-M coupling by considering the catalytic cycle (Scheme [1], top). When a tert-alkyl halide couples with an organoboron compound in the presence of a transition-metal catalyst (M), oxidative addition of M to the C_sp3–X bond leading to a C_sp3–M–X is problematic due to the steric hindrance of tert-alkyl halide. Even if the oxidative addition occurs smoothly, rapid β-hydrogen elimination from the resulting σ-alkyl metal intermediate (A)[2] can inhibit the main pathway to produce the coupling product via reductive elimination of B. However radical technology has recently been employed to successfully achieve tert-alkylative S-M couplings (Scheme [1], bottom), via the following pathway: (1) transmetalation between a metal catalyst and an organoboron compound leading to a R–Mⁿ species (C); (2) single electron transfer (SET) from C to a tert-alkyl halide to generate a transient intermediate D, which gives tert-alkyl–M ⁿ⁺²–R (E); (3) reductive elimination from E to give the cross-coupling product. In this paper, we would like to summarize recent progress in the development of tert-alkylative S-M couplings. S-M couplings with tert-alkyl electrophiles or tert-alkyl boron reagents will both be discussed.

Ni-Catalyzed tert-Alkylative Couplings

The first report on tert-alkylative S-M reaction was established by Fu’s group (Scheme [2]).[3] They found a reactive Ni catalyst (NiBr₂·diglyme/4,4′-di-tert-butyl-2,2′-bipyridine (Ligand 2)) for the coupling of tert-alkyl bromides or chlorides (2.1) and Ar(9-BBN) (where 9-BBN: 9-borabicyclo[3.3.1]nonane) (2.2) to produce 2.3a–d. Under the conditions, highly bulky tertiary alkyl electrophiles including a simple tert-butyl group (2.3a), 3-ethylpentane (2.3b), and chloro or olefin substituted alkyl groups (2.3c or d) can be used for S-M couplings. The authors proposed that a radical mechanism was operating that would avoid slow oxidative addition between the tert-alkyl electrophile and the catalyst and β-H elimination of the alkyl metal intermediate. As shown in Scheme [2], this reaction mechanism involves (1) transmetalation between Ni(I) and 2.2 to produce 2A, (2) SET from 2A to 2.1 to produce 2B and 2C, and finally (3) reductive elimination of 2D to give 2.3. Evidence of a radical process included the detection of diarylmethane as a side product. When the reaction was carried out in toluene, a significant amount of diarylmethane was obtained. In this side reaction, 2C could abstract a H-atom from toluene to produce a benzyl radical. Reductive elimination from an aryl–Ni(III)X–benzyl complex would produce diarylmethane. Further proof of a radical reaction included racemization of 2.4 during the S-M coupling of 2.2 and 2.4, as would be expected for radical generation from 2.4.

A Ni catalyst is also effective for bicyclic electrophiles. Arisawa and Shuto’s group reported S-M coupling of racemic cyclopropane-derived bicyclic iodide 3.1 and aryl boronic acid 3.2 in the presence of Ni(PCy₃)₂Cl₂ as a catalyst (Scheme [3]).[4] In this case, the authors successfully employed easily available aryl boronic acids as the aryl source to produce coupling products 3.3a–d in good yields.

Notably, the authors accomplished the first stereospecific S-M couplings using chiral iodocyclopropane 3.4 to produce 3.5, which can be transformed into chiral diol 3.6. They speculated that the reaction mechanism involves a radical process, but that racemization was suppressed due to the rigid structures of the alkyl electrophiles 3.1 and 3.4. The rigid cyclic siloxane structure may prevent racemization during the radical reaction.

A Ni catalyst can be applied to S-M reactions with tertiary benzylic and allylic sulfones, as reported by Nambo and Crudden’s group (Scheme [4]).[5] Organic halides are usually the best coupling partners for S-M couplings, whereas organic sulfones 4.1 bearing alkyl groups on the benzylic carbon, which have a tertiary alkyl moiety, are rare. In this reaction, the authors found that BrettPhos (L4a) or Doyle’s phosphines (L4b) were the most effective ligands for the tert-alkylative S-M couplings of 4.1 and 4.2. Arylboronic acids were reactive but arylboroxines 4.2 gave much higher yields of 4.3a–d. Naphthyl and allyl substituted alkyl sulfones were reactive but phenyl substituted alkyl sulfones were sluggish. The reaction mechanism is not clear, but the authors speculated that the formation of a π-benzyl nickel intermediate is required for smooth couplings.

Pd-Catalyzed tert-Alkylative Couplings

Fu’s group reported the first successful S-M couplings in the presence of a Ni catalyst. The first use of a Pd catalyst was reported by Harris’s group (Scheme [5]).[6] They used a 1-heteroaryl-3-azabicyclo[3.1.0]hexane fragment 5.2 as a tert-alkyl source on a boron. 1-Heteroaryl-3-azabicyclo[3.1.0]hexane fragments can be seen in a number of drug candidates with broad biological activity. The authors used cataCXium A catalyst (5) but 1,1'-bis(diphenylphosphino)ferrocene (dppf) was also effective to obtain good yields of 5.3. Under the optimized conditions, various 5.1 and 5.2 compounds were coupled together to produce 5.3a–d. The couplings were limited to bicyclic borons but heteroaryl halides can be applicable to the reaction (5.3c and 5.3d).

The cataCXium A catalyst (5) was also effective for carrying out S-M couplings with cyclopropyl substituted tertiary trifluoroborates (Scheme [6]).[7] The reaction of 6.1 and 6.2 in the presence of 5 gave gem-diaryl substituted cyclopropanes 6.3a–d in moderate to good yields. Aryl, heteroaryl and vinylic halides can be employed for the couplings. gem-Bis(boryl)cyclopropanes 7.4 were also good substrates, in which one boryl group can be coupled with 7.1 to give a borylcyclopropane product.

Grygorenko’s group demonstrated parallel synthesis of alkylated compounds libraries using the cataCXium A catalyst (5) (Scheme [7]).[8] In the synthesis, the reaction of heteroaryl bromides 8.1 and bicyclic trifluoroborates 8.2 gave the desired coupling products 8.3a–c. These results showed useful functional group compatibilities for medicinal chemistry in the tert-alkylative S-M couplings under cataCXium A catalyst (5) conditions.

Bicyclo[1.1.1]pentane motifs are not only an attractive tertiary alkyl source but also an important structure in medicinal chemistry and materials science,[9] but S-M couplings of a bicyclo[1.1.1]pentane boron reagents are rare. Kanazawa and Uchiyama’s group reported convenient S-M couplings with the bicyclo[1.1.1]pentane boron reagent 9.1 (Scheme [8]).[10] The latter was reactive after tert-butyllithium activation to produce borate 9.2. The authors also tried to activate 9.1 with LDA, n-BuLi, PhLi, and MeLi, but tert-butyllithium­ was most effective. Although addition of a stoichiometric amount of Cu₂O was necessary for smooth S-M couplings, the reason was unclear. Under the optimized conditions, the desired coupling products 9.4a–d were obtained in moderate to good yields in the presence of PdCl₂(dppf) as catalyst.

Hughes and Walsh’s group reported S-M couplings with various cyclic and bicyclic boron reagents 10.2 under Pd(OAc)₂/cataCXium A (10) conditions (Scheme [9]).[11] Similar to previous reports shown in this section, the desired coupling products 10.3a–d were obtained. Cu₂O was also necessary to improve the yield of couplings. As shown in Scheme [8, a] coupling with a bicyclo[1.1.1]pentane boron reagent required t-BuLi as an activator, but aqueous Cs₂CO₃ was enough to activate 10.2, in this case probably due to high temperature compared with the conditions shown in Scheme [8].

Although Pd catalysts are typical for S-M couplings, only cyclic boron reagents possessing a tert-alkyl moiety can be applied in the reactions. tert-Alkyl electrophiles cannot be used with Pd catalysts. In comparison to Ni, Pd catalyst systems are not reactive enough for tert-alkylative S-M couplings. This may be due to fast β-hydrogen elimination of the intermediate.

Fe-Catalyzed tert-Alkylative Couplings

Ni and Pd salts are good catalysts for some tert-alkylative S-M couplings, but less toxic and more earth-abundant iron is also a potential active catalyst for the couplings. Byers’ group reported S-M couplings with tert-alkyl chlorides (Scheme [10]).[12] In this case, an iron complex containing deprotonated cyanobis(oxazoline) ligand (11) was effective. Although couplings with primary- and secondary-alkyl halides resulted in high yields of the corresponding products, tert-alkyl chlorides 11.1 gave low yields. According to their reaction mechanism, the iron-amide complex 11A reacts with the arylboronic ester 11.2 to produce aryl iron species 11B. The formation of 11A could facilitate transmetalation between 11A and 11.2 due to inhibition of catalyst aggregation. After SET from 11B to 11.1 followed by the reaction of 11D and 11C, the corresponding coupling product 11.3 is generated. The reason for the low yields of 11.3a and 11.3b were not clear.

Byers’ group developed the iron-catalyzed tert-alkylative S-M coupling process by using an iron catalyst, but the yields were not satisfactory. In subsequent work they discovered an iron complex containing a β-diketiminate ligand 12 for tert-alkylative S-M couplings (Scheme [11]).[13] The purpose for this catalyst design was to (1) avoid catalyst aggregation and (2) achieve smooth transmetalation. Catalyst 12 has bulky substituents (t-Bu) and an electron-rich ligand structure, which improves the catalyst function. Under their optimized conditions, S-M couplings of 12.1 and 12.2 afforded good yield of the products 12.3a–d. In this reaction, both cyclic and acyclic tert-alkyl halides can be applied to the reaction under extremely mild conditions.

tert-Alkylative Couplings with 1-Alkenyl Borons

Coupling of a tertiary alkyl group with a terminal alkene is very difficult to accomplish, as traditional S-M cross-couplings cannot usually be applied to the synthesis of tert-alkylated­ alkenes, as noted above. Nishikata’s group established a ‘hybrid reaction system’ concept, which is a combination of two different active species, which can readily be exploited to accomplish S-M couplings of tertiary alkyl halides 13.1 and 1-alkenyl borons 13.2 (Scheme [12]).[14] The reaction of 2-bromoester 13.1 as a tert-alkyl source and 1-alkenylboronic ester 13.2 gave the corresponding cross-coupled product 13.3 in the presence of a copper/Ligand 13 catalyst. In this reaction, two active species are generated, a radical and an organometallic species, as shown in the mechanism. A tertiary alkyl radical 13B is generated from reaction of the Cu salt and 13.1 via a SET process from a 1-alkenylcopper species 13A that is generated from transmetalation of 13.2. These two active species are coupled to generate 13.3 after the reductive elimination of 13C. The reaction did not proceed in the presence of TEMPO, suggesting the intermediacy of radicals. The key to the success of this reaction is to avoid both oxidative addition and β-hydrogen elimination in the catalytic cycle. Indeed, an isolated 1-alkenylcopper species 13.4, which is generated from transmetalation between 13.2 and 13.5, smoothly reacted with 13.1 to produce 13.3. Another possible mechanism could involve an addition/elimination pathway but the addition of tertiary alkyl radicals to internal olefins is generally difficult. The reaction scope was very broad and 13.3a–d were obtained in good yields. A Pt co-catalyst was sometimes required, but its role was unknown.

tert-Alkylative Couplings under Photoirradiation

Ni, Pd, and Cu salts are good transition-metal catalysts for some classes of tert-alkylative S-M couplings using a tert-alkyl electrophile or tert-alkyl boron. One of the keys to success for tert-alkylative S-M coupling is the smooth generation of tert-alkyl radical species. Therefore, photoirradiation is another option for this purpose, because photocatalyst systems are suitable for the generation of radicals via SET from exited species.[15]

Sheikh and Leonori’s group found that eosin Y (EY), acting as a photoredox catalyst, efficiently catalyzed tert-alkylative S-M couplings of dicarbonyl bromides 14.1 and 1-alkenyl trifluoroborates 14.2 under green LED irradiation (Scheme [13]).[16] The reactions proceeded smoothly with tert-alkyl bromides and iodides, but the corresponding chlorides were sluggish. Under the conditions, 14.3a–d were obtained in moderate to good yields. The reaction starts with the excitation of EY by photoirradiation. tert-Alkyl­ radical 14A is generated from the reaction of excited EY (EY*) and 14.1 with concomitant formation of an EY cation radical that reacts with amine to regenerate EY. 14A adds to 14.2 to afford 14B. The authors speculated that 14A reacts preferentially at the ipso-C of 14.2 owing to the higher spin density. Finally, 14.3 is obtained after oxidation/ elimination of 14B.

Ryu’s group also reported tert-alkylative S-M couplings with styrylboronic acid under photoirradiation (Scheme [14]).[17] They used a Pd/phosphine catalyst as a photosensitizer for the coupling of 15.1 and 15.2. Although the reaction with primary- and secondary alkyl iodides worked smoothly with 1-alkenyl boronic acids, 1-adamantyl iodide (15.1) was applicable to the tert-alkylative S-M coupling (75% yield of 15.3). Additionally, arylboronic acid was used as a coupling partner for 15.1, and 50% yield of arylated adamantane was obtained. They proposed two mechanisms: path (A), radical addition to 15.2 followed by proton-elimination, and path (B), generation of R-Pd-I followed by transmetalation/reductive elimination. Both pathways could be possible, but path A is the most likely to proceed, considering the high steric bulk of 15.1. The authors also carried out the reaction in the presence of TEMPO, and no reaction was observed. On the other hand, the SET process appears to be followed by transmetalation and reductive elimination in the reaction for phenylation of 15.1 (path B).

Molander’s group reported Ir-catalyzed tert-alkylative couplings of aryl bromides 16.1 with tert-alkyl trifluoroborate salts 16.2 under blue LED irradiation (Scheme [15]).[18] The combination of a Ni(TMHD) catalyst and Ir catalyst 16 was important to give 16.3. Under their photoredox conditions, various functionalized tert-alkyl groups and aryl groups can be used, and moderate to good yields of 16.3a–d were obtained. ZnBr₂ improved the yield slightly but it was not a requirement. There two pathways to generate tert-alkylative­ coupling, but control experiments implied that the reaction via 16E could be the true pathway. In the reaction of stoichiometric 16A and 16.2, no coupling was observed. Considering this control experiment, the reaction starts with the generation of 16E via SET from Ni⁰. Transmetalation followed by reductive elimination of 16C provides 16.3. The resulting Ni^I species could be reduced to Ni⁰ by the Ir radical anion generated from the reaction of photoexcited Ir and 16.2.

VanHeyst and Qi’s group reported a similar Ni/Ir photoredox method for S-M couplings of bicyclo[1.1.1]pentane trifluoroborate salts 17.1 and aryl bromides 17.2 (Scheme [16]).[19] Under photoirradiation, various functionalized aryl bromides 17.2 can be coupled with 17.1 to produce 17.3a–d in moderate to good yields. Compared to the reactions shown in Schemes 8 and 9, the reaction conditions are mild, and functional group compatibilities are broad, which could be valuable for the synthesis of useful molecules like medicinal drugs.

Direct visible-light excitation of tert-alkyl borates was established by Sumida, Hosoya and Ohmiya’s group (Scheme [17]).[20] A photocatalyst system is one of the most powerful methodologies for the generation of alkyl radicals, but the oxidation/reduction steps of the photoredox catalyst often complicate the reaction. In this context, the authors developed a boracene-based alkylborate 18.1, which included a photosensitizer moiety. Under photoirradiation, a tert-alkyl radical is efficiently generated from 18.1 and the corresponding tert-alkylative S-M coupling occurred in the presence of a Ni catalyst. In this reaction, primary-, secondary- and tert-alkyl groups can be employed, and various tert-alkylated arenes 18.3a–d were synthesized in moderate to good yields. The reaction starts with the generation of a tert-alkyl radical species 18B via photoexcitation of 18.1. There are two pathways after the generation of 18B, but path B is likely to be preferable based on Molander’s results shown in Scheme [15]; namely, that 18D reacts with 18.2 to produce 18.3 after reductive elimination of 18C. The authors predicted the photophysical properties of 18.1; for tert-butylated 18.1 [E(18.1^•+/18.1*)] = –2.2 V vs. SCE in MeCN. This value is high enough to reduce Ni^II and Ni^I-Br.

Sumida, Hosoya and Ohmiya’s group also discovered a more efficient process for tert-alkylative S-M couplings with a boracene-based alkylborate (18.1 and 19.1) (Scheme [18]).[21] In the reaction shown in Scheme [17], they used a Kessil lamp as a light source, and the reaction time was 14 h. On the other hand, an upgraded reaction, shown in Scheme [18], employed a photochemical microreactor (weak light source) and shorter reaction time (1 h). The key to the success of this reaction is to use an Ir-photocatalyst (19). The authors described that a Kessil lamp (measured with a 1% transmittance neutral-density filter) showed more than 700 times higher irradiance at 440 nm than the photochemical microreactor. Under the optimized conditions, the reaction of 19.1 and 19.2 in the presence of Ni and Ir catalysts (19) under weak photoirradiation for 1 h afforded 19.2a–d in moderate to excellent yields.

Stereospecific tert-Alkylative Couplings

Chiral tert-alkyl fragments are attractive chiral sources for the construction of quaternary or tetrasubstituted carbon centres. There are many reports on catalytic asymmetric constructions of secondary- and tertiary-carbons via coupling reactions, whereas the corresponding chiral tert-alkylations are extremely difficult due to difficulty of chiral recognition of a bulky three-dimensional tert-alkyl fragment. On the other hand, stereospecific reactions of chiral tert-alkyl reagents provide another option to construct quaternary centres. In the case of tert-alkylative S-M couplings, the key intermediate is a tert-alkyl radical, in which chiral information is typically lost. Stereospecific coupling is, therefore, challenging. Indeed, Fu’s group employed a chiral tert-alkyl electrophile (2.4) shown in Scheme [2] but obtained a racemic product.

Watson’s group successfully developed stereospecific tert-alkylative S-M couplings of chiral tert-benzylic acetates 20.1 and 20.2 in the presence of a Ni catalyst (Scheme [19])[22] (%es = product % ee / substrate % ee; ee: enantiomer excess, es: enantiospecificity). The reaction provided stereoretentive products 20.3a–d in high yields with excellent enantiospecificity (es). Using a tert-benzylic acetate is very important for the stereospecific coupling. The retention of stereochemistry in the product could be attributed to a directed S_N2′ oxidative addition (20A) to produce 20B, which has been proposed for stereoretentive cross couplings of secondary benzylic and allylic electrophiles.[23] A naphthyl substituent is required to accomplish this reaction.

By using tert-benzyl pivalates 21.1 in combination with a stilbene ligand 21, Watson’s group overcame the ‘naphthyl requirement’ of their previous study, as shown in Scheme [20].[24] Chiral benzylic pivalates 21.1 reacted smoothly with 21.2 to produce 21.3a–d in good yields with excellent es. They speculated that the low es for the reaction of 21.1 under their previous conditions could be attributed to a difficult oxidative addition reaction. Contrastingly, the previous high es with naphthyl substrates 20.1 could be attributed to oxidative addition via an S_N2′ mechanism. To enhance the reactivity of benzylic substrates 21.1, they used a less bulky ligand 21. The latter could also stabilize a Ni⁰ species, which is expected to undergo smooth oxidative addition of 21.1.

Stereospecific S-M coupling with chiral tert-alkyl electrophiles was established by Watson’s group, whereas the corresponding coupling with chiral tert-alkyl boron reagents has not yet been described. Yamamoto and Suginome’s group reported stereospecific intramolecular S-M coupling with a trisubstituted alkyl boron (22.1) in the presence of a Cu catalyst and ligand 22 (Scheme [21]).[25] Although this example is an intramolecular reaction, the reactions of 22.1, possessing chiral trisubstituted alkyl groups, afforded products 22.2a–d, with inversion of the stereochemistry, in excellent yields and selectivities. The origin of the stereoinversion could be attributed to the transmetalation step. The transmetalation is reasonably explained by attack by an electrophilic copper(I) species from the backside of the boron atom at the stereogenic carbon atom (22TS). This backside attack is preferred due to the steric congestion at the frontside because of intramolecular coordination of the amide carbonyl to the boron atom. After the transmetalation, a chiral alkyl copper intermediate 22A then probably undergoes oxidative addition to give 22B. Finally, 22.2 is obtained via reductive elimination of 22B.

Conclusion

In this review, we have summarized progress on tert-alkylative S-M couplings. The reactions are catalyzed by Ni, Pd, Fe, Cu, and photocatalysts, and involve the generation of tert-alkyl radicals from tert-alkyl electrophiles or tert-alkylborons in the reaction. To generate the key intermediate tert-alkyl radicals from tert-alkyl boron, direct reagent activation or boracene photoactivation can also be used. Although generation of a tert-alkyl radical is necessary, stereospecific tert-alkylative S-M couplings have nevertheless been reported using chiral tert-alkyl electrophiles and boron reagents. In these cases, stereospecific oxidative addition or transmetalation is required to accomplish efficient coupling. The tert-alkylative couplings shown in this review are very effective, but substrate specificity and functional group compatibilities remain outstanding challenges in this research area.[26]

Conflict of Interest

The authors declare no conflict of interest.

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Corresponding Authors

Publication History

Received: 15 December 2021

Accepted after revision: 05 January 2022

Accepted Manuscript online:
05 January 2022

Article published online:
15 February 2022

© 2022. Thieme. All rights reserved

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