Abstract
This report provides a brief overview of the various representative literature procedures for the synthesis of 1,5-disubstituted tetrazoles (1,5-DSTs) and fused 1,5-disubstituted tetrazoles with more than 120 references. Most of the published methods for the synthesis of 1,5-DSTs include the use of nitriles, amides, thioamides, imidoyl chlorides, heterocumulenes, isocyanates, isothiocyanates, carbodiimides, ketenimines, ketones, amines, and alkenes as the starting materials. The transformation of 1- and 5-substituted tetrazoles into 1,5-DSTs is also covered in this report.
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Introduction
Tetrazoles are a representative class of poly-aza-heterocyclic compounds, consisting of a 5-membered ring of four nitrogen and one carbon atoms. They are unknown in the nature. Tetrazoles, based on the number of the substituent, are divided into three categories (Scheme 1): (i) parent tetrazoles (simplest tetrazoles), (ii) monosubstituted tetrazoles (1-, 2-, or 5-substituted), and (iii) disubstituted tetrazoles (1, 2-, or 2,5-disubstituted).
Recently, the tetrazole ring has attracted significant attention, especially among medicinal chemistry. While 5-substituted tetrazole is an isosteric replacement for carboxyl group, 1,5-disubstituted tetrazoles (1,5-DSTs) are isosteres for the cis-amide bond in peptides [1]. These substituents have displayed similar types of biological activity because of their physicochemical properties, though they are structurally different. Moreover, replacement of the cis-amide bond by 1,5-DSTs enhances metabolic stability [2]. Marshall and Zabrocki [2–4] have shown that peptides with a 1,5-DST unit, as in B, may be effective conformational mimics for the corresponding peptides that prefer to adopt a cis-amide bond conformation [5–7], or which need to preorganize the amide bonds to act as enzyme substrates, as in A (Scheme 2).
1,5-DST moieties are found in numerous biologically active substances. Some of these scaffolds exhibit various types of biological properties, such as anti-inflammatory (C) [8], antiviral (i.e., HIV) (D) [9], antibiotics (E) [10], anti-ulcer (F) [11], anxiety (G) [12], anti-tubercular (H) [13], and anti-hypertensive agents (I) [14, 15]. The \({\upbeta }\)-lactam antibiotics of the cephalosporin class (J) [16, 17] is an example of drugs containing a 1,5-DST moiety. Cephalosporin and its analogs are comparable with penicillin in structure and activity trend. Such antibiotics have low toxicity and a wide range of activity (Scheme 3).
Tetrazole classifications
1,5-DSTs as cis-amide surrogates
Examples of biologically active substances containing a 1,5-DST
To this day, several excellent review articles on syntheses or medicinal chemistry aspects of tetrazoles have been published [13, 18–22]. This review summarizes the recent synthetic pathways that have been explored for the production types of 1,5-DSTs, with particular focus most recent contributions to the field. The many published preparative methods for the synthesis of 1,5-DSTs include the use of nitriles, amides, thioamides, imidoyl chlorides, heterocumulenes (e.g., isocyanates, isothiocyanates, carbodiimides, and ketenimines), ketones, amines, and alkenes as the starting materials.
In addition, other studies for the preparations of 1,5-DSTs including the transformation of the 1- and 5-substituted tetrazoles into 1,5-DSTs are also covered in this report.
1,5-DSTs syntheses from nitriles
The synthesis of tetrazoles by the Huisgen 1,3-dipolar cycloaddition reaction between nitriles and azides (azide ion or hydrazoic acid) is a well known process. However, the reaction of nitriles with organic azides is limited in scope because only nitrile substrates with strong electron-withdrawing groups can successfully react as the dipolarophilic partners with organic azides. These groups have a tendency to lower the LUMO of the nitriles and thus enhance the interaction with the HOMO of the azide [23].
In 1962, Carpenter established that intermolecular condensation between nitriles and organic azides can be completed in the absence of any catalyst if the nitrile is suitably activated by electron-withdrawing groups [24]. Diverse nitriles with electron-withdrawing groups and organic azides were used in this process at higher temperatures leading to the formation of 1,5-DSTs (Scheme 4).
Synthesis of 1,5-DSTs via reaction between nitriles and organic azides
In 2002, Demko and Sharpless reported the synthesis of various 1,5-DSTs by the coupling reaction of p-toluenesulfonyl cyanide (TsCN) with aromatic and aliphatic azides under solvent-free conditions (Scheme 5) [25]. In the reaction, only 1,5-DST isomers of less sterically hindered azides were observed in nearly quantitative yields (entries 1–6).
Synthesis of 1,5-DSTs
In a later report, the same authors modified their protocol for the synthesis of 1,5-DSTs 7 using acyl cyanides 6 instead of TsCN 4 (Scheme 6) [26]. This synthetic method provides advantages, such as high yields and simple workup procedure. It was also found that p-nitrophenyl cyanoformate could be used in the same process in excellent yield, and the resulting activated esters of the 1-alkyltetrazole-5-carboxylic acid could be reacted in situ with amines or alkoxides as nucleophiles.
Synthesis of 1,5-DSTs from acyl cyanides
Based on a similar intermolecular cycloaddition reaction, Dondoni and co-workers have developed an efficient and a click way for the formation of 1-glycosylmethyl-5-tosyl tetrazoles 9 [27] from the reaction of benzylated or acetylated glycosylmethyl azides (azidomethyl glycosides) 8 with TsCN (4) at 100 \(^{\circ }\hbox {C}\) (Scheme 7).
Reaction of glycosylmethyl azides with TsCN
Bosch and Vilarrasa reported a click reaction between organoazides and nitriles in the presence of 1–10 mol% of soluble \(\hbox {Cu}_{2}\hbox {(OTf)}_{2}{\cdot }\hbox {C}_{6}\hbox {H}_{6}\) catalyst. In most of the cases, 1,5-DSTs were obtained in excellent yields in \(\hbox {CH}_{2}\hbox {Cl}_{2}\) at ambient temperature (Scheme 8). The temperature of the reactions was increased by 60–110 \(^{\circ }\hbox {C}\) compared to the analogous reaction in the thermal activation and absence of catalyst conditions (see Schemes 4, 5, 6, 7). However, under catalytic conditions, minor amounts of the 2,5-disubstituted regioisomers were also obtained [28].
\(\hbox {Cu}_{2}\hbox {(OTf)}_{2}\)-catalyzed cycloaddition reaction between nitriles and organic azides
The 1,3-dipolar cycloaddition reaction of organomercury(II) azides 11 with organonitriles 2 was described by Klapotke et al. [29]. This reaction provides advantages including highly regioselective, mild conditions, without the need of a catalyst, quantitative yields, and simple workup procedure (Scheme 9).
Synthesis organomercury(II) tetrazoles
Nasrollahzadeh and co-workers have developed useful catalytic protocols such as \(\hbox {ZnCl}_{2}\) under aqueous refluxing conditions [30], \(\hbox {FeCl}_{3}{-}\hbox {SiO}_{2}\) [31], and natrolite zeolite [32] for the preparation of 1-aryl-5-amino-1H-tetrazole derivatives 14 from arylcyanamides 13 and hydrazoic acid or \(\hbox {NaN}_{3}\) (Scheme 10). Upon exploration of the reaction scope, it was revealed that an electron-releasing substituent on the arylcyanamide was essential for the attainment of stereoselectivities. On the other hand, an arylcyanamide with an electron-releasing substituent led to 1-aryl-5-amino-1H-tetrazole 14; however, the reaction was in some cases hampered by the formation of 5-arylamino-1H-tetrazole 15 as other regioisomeric products.
Synthesis of aminotetrazoles
Intramolecular [\(3+2\)] cycloaddition reaction of organic azides and nitriles gives access to fused 1,5-DSTs products in high yields. When the two functional groups involved (azide and nitrile) belong to the same molecule, the cycloaddition of rates can be greatly enhanced. The preparation of fused polycyclic 1,5-DSTs via intramolecular [\(3+2\)] cycloaddition reaction is exemplified by different research groups. The first report of this cycloaddition reaction of organic azides and nitriles was by Kereszty [33]. In this report acid-catalyzed cyclization of a series of azidoalkyl cyanides 16 forms fused polycyclic 1,5-DSTs 17 (Scheme 11).
The first intramolecular cycloaddition reaction of organic azides and nitriles
Smith et al. [34] have described the thermal intramolecular cyclization reaction of 2-azido-2\(^{\prime }\)-cyanobiphenyl (18) to form tetrazolophenanthridine (19) in good yield and purity (Scheme 12). Tetrazolophenanthridine was found to have excellent stability to heat decomposing above 300 \(^{\circ }\hbox {C}\), while nearly all tetrazoles lose their nitrogen at above 200 \(^{\circ }\hbox {C}\).
Synthesis of tetrazoloplienanthridine
Tetrazoles derived from d-manno and d-rhamnofuranose [35, 36] and d-manno and d-rhamnopyranose [37] were made via the intramolecular cycloaddition reaction of azide and nitrile groups in the acyclic precursors 20 and 22 forming bicyclic tetrazoles 21 and 23 in good yields. These tetrazoles are inhibitors of human liver \({\upalpha }\)-mannosidase (Scheme 13).
Synthesis of furanotetrazole and pyranotetrazole
Diverse azidoheteroatom-substituted nitriles 24 underwent intramolecular [\(3+2\)] cycloadditions producing tetrazoles fused to saturated or unsaturated five- or six-membered ring structures 25 bearing nitrogen, oxygen, or sulfur heteroatoms (Scheme 14) [38].
Intramolecular cycloaddition of azidoheteroatom-substituted nitriles
Another illustration of this approach is found for the preparation of novel substituted oxabicyclic tetrazoles 27 from the intramolecular cycloaddition of 3-azido-2-aryl-1,3-dioxolanes and the corresponding 1,3-dioxanes 26 in the presence of TMS-CN and \(\hbox {BF}_{3}{\cdot }\hbox {OEt}_{2}\) in \(\hbox {MeNO}_{2}\) at 0 \(^{\circ }\hbox {C}\) [39]. Cis-substituted bicyclic tetrazoles 27 were formed as the major isomers in good to excellent yields. Electron-donating groups on the aromatic rings usually led to high yields. These thermodynamically controlled enantiopure products represent a new aspect of proximity-assisted dipolar cycloadditions through discrete oxocarbenium ion intermediates (Scheme 15).
Formation of oxabicyclic tetrazoles
Couty et al. reported a route to fused tetrazole–piperazines 29 based on an intramolecular [\(3+2\)] cycloaddition. The reaction between chlorides 28 or 30 with \(\hbox {NaN}_{3}\) in DMSO at 150 \(^{\circ }\hbox {C}\) resulted in the formation of the fused tetrazole 29 in good yields [40]. Interestingly, the phenyl ring bearing chlorides 28 provided only a single isomer 29 while in the case of chlorides 30 a mixture of separable regioisomers 31 and 32 is produced almost equivalently. A plausible reaction mechanism is shown in Scheme 16. First, it involves the generation of an aziridinium intermediate K followed by a regioselective ring opening at the benzylic position of chloride 28 and at 2 potential positions of 30 to give azide L products. After that, these intermediates undergo an intramolecular cycloaddition reaction with the nitrile part of the molecule to provide the corresponding tetrazole–piperazines.
Synthesis of fused tetrazole–piperazines
A new dibutyltin oxide (\(\hbox {Bu}_{2}\hbox {SnO}\))-catalyzed reaction involving allylic bromides and azidotrimethylsilane (TMS-\(\hbox {N}_{3}\)) has been developed by Ek et al. (Scheme 17) [41]. This process included the cycloaddition reaction of a nitrile and TMS-\(\hbox {N}_{3}\) and followed by intramolecular N-allylation.
Preparation of fused tetrazoles
Cyclization of the 2-azidomethyl-3-cyanopyridines 34 upon heating in toluene solution at 130–140 \(^{\circ }\hbox {C}\) provided the desired heterocyclic structures containing a 3-(tetrazol-5-yl)pyridine 35 in good yields (Scheme 18) [42]. Here the authors mentioned that high purity and low concentration of the azides 34 were essential for a successful cyclization. Moreover, the reaction time can be shortened (2–4 h) by heating the reaction at the same temperature using microwave irradiation [43].
Synthesis of heterocyclic structures containing a 3-(tetrazol-5-yl)pyridine
The one-pot three component reaction of 4-chloro-3-formyl-coumarins 36, \(\hbox {NaN}_{3}\), and alkyl/aryl acetonitriles 37 gave the corresponding tetrazole-fused pyrido[2,3-c]coumarin derivatives 38 (Scheme 19). The reaction pathway presumably involves the condensation of compound 36 with 37 to form intermediate M which then reacted with \(\hbox {NaN}_{3}\) to afford intermediate N, which immediately cyclized to give 38 in high yields [44].
Preparation of tetrazole fused pyrido[2,3-c]coumarin derivatives
1,5-DSTs syntheses from amides and thioamides
An amide or thioamide bond can be transformed into a tetrazole via imidoyl chloride and imidoyl azide intermediates. Several reagents can be used to convert amides or thioamides into their corresponding imidoyl chlorides, such as reagents are \(\hbox {PC1}_{5},\,\hbox {PCl}_{3},\,\hbox {POCl}_{3},\,\hbox {SOCl}_{2}\), and oxalyl chloride.
In 1987, Yu and Johnson employed \(\hbox {PCl}_{5}/\hbox {HN}_{3}\) for the conversion of amides 39 into corresponding tetrazoles 40 (Scheme 20) [5] where they emphasized that the success of the reaction was dependent on the employed amino protecting group and also the amino acid sequence of the starting dipeptide. In addition, in the presence of a base, the racemization of the \({\upalpha }\)-carbon atom of the N-terminal and C-terminal residues of the tetrazole peptides was observed.
Preparation of tetrazole dipeptides using \(\hbox {PCl}_{5}\) and \(\hbox {HN}_{3}\)
Sipeptides 41 were was reacted with \(\hbox {PCl}_{5}\) in the presence of quinoline at room temperature forming imidoyl chloride intermediate [45]. This intermediate reacts (in situ) with a benzene solution of \(\hbox {HN}_{3}\) to produce \({\upalpha }\)-methylene tetrazole-based dipeptides 42 (Scheme 21). An X-ray crystal structure determination of dipeptidomimetic 42 revealed that its solid state structure and conformation is well clear and resembles that of the bioactive cis-like conformation of nucleus isostere of JG-365, a potent inhibitor of HIV protease [46].
Synthesis of \({\upalpha }\)-methylene tetrazole-based dipeptides
A mild and general one-pot process for the transformation of cyanoethyl amides 43 to cyanoethyl-protected tetrazoles 44 with TMS-\(\hbox {N}_{3}\) via the intermediacy of imidoyl chlorides generated in situ with \(\hbox {PCl}_{5}\) has been described (Scheme 22). This synthetic sequence differs from other methods in that it employs pyridine to trap the hydrogen chloride generated during the imidoyl chloride formation with \(\hbox {PCl}_{5}\). This transformation is tolerated by a variety of functional groups, is amenable to use with acid-sensitive functionality, and efficiently converts sterically hindered amides. Furthermore, the reaction does not require hydrazoic acid or azide salts, and has the added advantage of being performed in a one-pot manner [47]. The transformation of cyanoethyl amides to cyanoethyl tetrazoles has also been achieved with \(\hbox {PPh}_{3}\), diethylazodicarboxylate (DEAD), and TMS-\(\hbox {N}_{3}\) [48].
Conversion of cyanoethyl amides to cyanoethyl tetrazoles
The diaryl amide derivatives 45 are ideally suited for the synthesis of the 1,5-diaryl-substituted tetrazoles 46 [49]. In this case, amides 45 are treated with \(\hbox {SOCl}_{2}\) under refluxing conditions to give the corresponding imidoylchloride intermediates. Treatment of imidoyl chlorides with an excess of \(\hbox {NaN}_{3}\) gave 1,5-diaryl-substituted tetrazoles 46 in good to excellent yields (Scheme 23). It was also found that \(\hbox {SiCl}_{4}/\hbox {NaN}_{3}\) could promote the preparation of 1,5-diaryl-substituted tetrazoles from diaryl amides [50].
Preparation of 1,5-diaryl-substituted tetrazole derivatives
Amides 47 were converted to imidoyl chlorides with \(\hbox {(COCl)}_{2}\) in the presence of quinoline and then reacted with \(\hbox {NaN}_{3}\) in DMF at 60 \(^{\circ }\hbox {C}\) to form the corresponding benzyloxy protected tetrazoles 48 (Scheme 24) [51].
Synthesis of benzyloxy protected tetrazoles from amides using \(\hbox {(COCl)}_{2}\)
Linear \(\hbox {N}^{\omega }\)-tritylated \(\omega \)-amino thiobenzylamides and \(N^{{\upalpha }}\),\(N^{\omega }\)-ditritylated polyamino mono- or bis-thioamides were transformed to the corresponding tetrazole derivatives 50 and 52 by TMS-\(\hbox {N}_{3}\) under Mitsunobu reaction conditions (Scheme 25) [52]. The activation of amides and thioamides for nucleophilic attack by \(\hbox {PPh}_{3}\)–diisopropylazodicarboxylate (DIAD) is called the Mitsunobu reaction [53].
Synthesis of polyamines incorporating tetrazole rings
Schroeder et al. improved the reaction conditions for the transformation of amides to the corresponding disubstituted tetrazoles [54]. As it can be seen in Scheme 26, most of the sterically hindered amides are efficiently transformed to their corresponding tetrazole derivatives using diphenylphosphoryl azide (DPPA), DIAD, and diphenyl(2-pyridyl)phosphine.
A general route for the preparation of 5-aminotetrazoles was developed by Batey and Powell [55]. In this procedure, amines react with isothiocyanates leading to thioureas 57. Then, the obtained thioureas reacted with mercury(II) chloride and \(\hbox {NaN}_{3}\) to provide the corresponding 5-aminotetrazoles in excellent yields. A plausible mechanism for this reaction involves coordination of Hg(II) with thioureas to furnish O, which followed by attack of an azide anion gives intermediate guanyl azide P. The latter upon electrocyclization would render the 5-aminotetrazole 50 (Scheme 27). This method has been extended to the synthesis of mono-, di-, and trisubstituted 5-aminotetrazoles. Another approach has been used for the synthesis of 1,5-DSTs from the thioamides [56] where thioamides react with mercury(II) salts and TMS-\(\hbox {N}_{3}\) to give the corresponding tetrazoles.
Preparation of 1,5-DSTs from hindered amides
The methylated sulfur atom of a thioamide acts as a leaving group in the nucleophilic displacement. Atherton and Lambert had used this strategy to introduce an azide group so that the resulting azido amine can produce the corresponding tetrazole via electrocyclic ring closure [57]. This method was recently used for the synthesis of tetrazole 60 from the methylated sulfur atom of 4-[2-(acetoxy)ethyl]-2-methylthiosemicarbazide (59) with \(\hbox {NaN}_{3}\) (Scheme 28) [58].
Another interesting method for conversion of an amide to 1,5-DSTs was used by Ostrovskii and co-workers [59–61]. In this method, treatment amides with tetrachlorosilane \((\hbox {SiCl}_{4}){-}\hbox {NaN}_{3}\) leads to the formation of 1,5-DST derivatives. The authors demonstrated that treating amino acids 61 with \(\hbox {SiCl}_{4}/\hbox {NaN}_{3}\) gives the tetrazole-containing derivatives 62 (Scheme 29).
Cyclopropyldiazonium intermediates were generated from the reaction of N-cyclopropyl-N-nitrosourea (63) with bases. The 1,5- and 2,5-DSTs 64 and 65 were obtained from the treatment of N-cyclopropyl-N-nitrosourea with a MeONa solution in methanol or an aqueous solution of KOH at \(-10\) to 0 \(^{\circ }\hbox {C}\) [62]. It seems that the formation of tetrazoles 64 and 65 formally involves an interaction of two diazocyclopropane molecules and a methanol or water molecule (Scheme 30).
Recently, a new and expedient strategy for the regioselective synthesis of 5-aminotetrazole derivatives 67 during oxidative desulfurization of corresponding 1,3-disubstitutedthioureas 66 was reported by the Telvekar group [63]. The reaction was carried out with combinations of iodobenzene, oxone, triethylamine (\(\hbox {Et}_{3}\hbox {N}\)), and \(\hbox {NaN}_{3}\) at room temperature. The best result was achieved when iodobenzene, oxone, \(\hbox {Et}_{3}\hbox {N}\), and \(\hbox {NaN}_{3}\) were used in 2, 3, 3, and 3 equiv, respectively. The symmetrical and unsymmetrical 1,3-disubstitutedthioureas easily react to produce desired products in moderate to good yields. In the case of unsymmetrical thioureas, the formed products have the lower pKa amine nitrogen atom embedded into the ring and the higher pKa amine nitrogen atom appended as the exocyclic amino group (Scheme 31).
1,5-DSTs syntheses from imidoyl chlorides
In 1992, Zabrocki and co-workers demonstrated that N-substituted imidoyl chlorides underwent nucleophilic replacement by an azide ion which post-cyclization provided 1,5-DSTs [3].
Mercury(II)-promoted synthesis of 5-aminotetrazoles
Further investigations revealed that the preparation of 1-substituted-5-trifuoromethyltetrazoles 69 from N-substituted trifuoroacetimidoyl chlorides 68 could proceed in moderate to high yields in a building block approach (Scheme 32). As shown in Scheme 32, an electron-donating group on the N-substituent of 68 enhanced the yield of the product 69 [64].
The mechanism of the formation of 1,5-DSTs from the N-substituted imidoyl chlorides has been studied by Hegarty et al. [65]. The reaction of N-alkylbenzimidoyl chlorides 70 with azide ion gives initially imidoyl azides R (Z). Imidoyl azides are produced via nucleophilic trapping of the nitrilium cations Q (which could be observed by IR spectrum) in aqueous organic solutions. Subsequently, these azides rearrange to the more stable tetrazoles 71. The rate-determining step (RDS) of the reaction was the isomerisation of the firstly formed Z-isomer of the imine to the E-isomer as a result of imine nitrogen inversion. Therefore, a low dependence on the solvent polarity and insensitivity to the added salts were observed. The Hammett \(\rho \) value for the rearrangement of the imidoyl azides to the related tetrazole derivatives was \(-0.4\) confirming that the rate-determining step was the nitrogen inversion of the imine (Scheme 33).
Conversion of thio-methylated thioamide
Synthesis of tetrazole-containing amino acid derivatives
Synthesis of 1,5- and 2,5-DSTs
The reaction of imidoyl chlorides 72 with \(\hbox {HN}_{3}\) in dry benzene for 8 h successfully produced 1-aryl-5-methyl-1H-tetrazoles 73 [66]. Then, the reaction between 1-aryl-5-methyl-1H-tetrazoles 73 and 1,2-benzene S, which was formed by diazotization of 1,2-anthranilic acid in dry MeCN, leads to the generation of 1-aryl-5-benzyl-1H-tetrazoles 74 in good yields (Scheme 34).
A two-step approach was used for the preparation of 1H-tetrazoles 77, in which the initial anilines 75 were acylated with acyl chlorides. Then, the reaction of resulted acylanilides with phosphorus oxychloride (\(\hbox {POCl}_{3}\)) led to imidoyl chlorides 76 [67]. Lastly, a one-pot reaction of 76 with \(\hbox {NaN}_{3}\) gave the tetrazole rings 77 (Scheme 35).
Imidoyl chlorides were successfully generated from water-stable imidoylbenzotriazoles [68]. This approach was demonstrated by Katritzky and co-workers for the preparation of the 1,5-DSTs from imidoylbenzotriazoles [69]. In this approach, the reaction of imidoylbenzotriazoles 78 with \(\hbox {NaN}_{3}\) in the presence of trifluoroacetic acid (TFA) and a phase-transfer catalyst (tetrabutylammonium bromide (TBAB)) at 20 \(^{\circ }\hbox {C}\) for 30 minutes afforded the 1,5-DSTs 79 in good yields and short reaction times (Scheme 36).
1,5-DSTs syntheses from heterocumulenes
Heterocumulenes such as isocyanates, isothiocyanates, carbodiimides, and ketenimines react with an azide anion to directly cyclize to the tetrazolic compounds. The reaction of aryl isocyanates 80 with two molar amounts of TMS-\(\hbox {N}_{3}\) afforded l-aryl-5(4H)-tetrazolinones 81 in high yields. It is interesting to note that, when TMS-\(\hbox {N}_{3}\) reacted with benzoyl isocyanates 82 under similar conditions, 3-hydroxy-5-phenyl-1,2,4-oxadiazole 83 was resulted in good yields (Scheme 37) [70]. Moreover, the reaction of aryl isocyanates with TMS-\(\hbox {N}_{3}\) in dry benzene yielded l-aryl-5(4H)-tetrazolinones [71].
Preparation of 5-aminotetrazoles from 1,3-disubstituted thioureas
Preparation of 1-substituted-5-trifuoromethyltetrazoles
Treatment of aniline derivatives with \(\hbox {CSCl}_{2}\) gives thioisocyanates that can then react with \(\hbox {NaN}_{3}\) to provide tetrazoles as a mixture of tautomers. Finally, treatment with \(\hbox {Et}_{3}\hbox {N}\) smoothly converted the thione into the corresponding thiol products 84 (Scheme 38) [72].
In situ generated dialkylcarbodiimides from their corresponding \(N\),\(N'\)-dialkylthioureas were reacted with \(\hbox {HN}_{3}\) to afford l-alkyl-5-(alkylamino)tetrazoles in 32–78 % yields [73]. The reaction of \(N\),\(N'\)-alkyl(aryl)carbodiimide with TMS-\(\hbox {N}_{3}\) in dry benzene at 50–60 \(^{\circ }\hbox {C}\) produced a 1:l adduct, l-alkyl(aryl)-5-[N-(trimethylsilyl)tetrazoles 86, in 29–83 % yields. Desilylation of 86 with MeOH afforded 5-aminotetrazoles 87 in quantitative yields (Scheme 39) [70].
Suggested mechanism for the formation of 5-DSTs from N-substituted imidoyl chlorides
Generation of 1-aryl-5-benzyl-1H-tetrazoles
One-pot and two-step procedure for the synthesis of 1,5-DSTs
Imidoylbenzotriazole as a precursor for the synthesis of 1,5-DSTs
Reaction of isocyanates with TMS-\(\hbox {N}_{3}\)
Reaction of thioisocyanates with \(\hbox {NaN}_{3}\)
Reaction of dialkylcarbodiimides with TMS-\(\hbox {N}_{3}\)
Vorobiov et al. reported another interesting method for the preparation of 5-alkylamino-1-aryltetrazoles from in situ generated carbodiimides [74]. In their protocol, the aryltetrazoles 89 are prepared from the related aryltetrazolium salts 88 in two steps (Scheme 40). In the first step, tetrazolium salts 88 undergo ring-opening in the presence of DMSO, \(\hbox {Et}_{3}\hbox {N}{\cdot }\hbox {HCl}\), and \(\hbox {NaN}_{3}\). These salts decompose with elimination of \(\hbox {N}_{2}\) immediately form N-alkyl-\(N'\)-arylcarbodiimides T. In the next step, an azide ion attacks the carbodiimides T and an intramolecular cyclization furnishes 5-alkylamino-1-aryltetrazoles 89.
Preparation of 5-alkylamino-1-aryltetrazoles from in situ generated carbodiimides
The reaction of keteneimines 90 with TMS-\(\hbox {N}_{3}\) in tert-butanol gives phosphorylated tetrazoles 91 in fair to good yields [75]. It is assumed that in the formation of keteneimines 90 a condensation of isocyanides with acyl chlorides under solvent-free methods (isocyanide-Nef reaction) forms the corresponding imidoyl chloride and this is followed by the treatment with trimethyl phosphite (Scheme 41).
Reaction of keteneimines with TMS-\(\hbox {N}_{3}\)
A two-step process for the synthesis of 1,5-DSTs 93 containing a \({\upbeta }\)-siloxy or \({\upbeta }\)-sulfonamide group has been developed [76]. In this process, ketenimines 92 were first prepared via an isocyanide-based multicomponent reaction involving isocyanides, dialkylacetylenedicarboxylates, and triphenylsilanol or sulfonamide. Then, the resulting ketenimines 92 reacted with TMS-\(\hbox {N}_{3}\) to afford 1,5-DSTs (Scheme 42).
Preparation of 1,5-DSTs containing a siloxy or sulfonamide group
Another quite fascinating use of an intramolecular [\(3+2\)] cycloaddition reaction was demonstrated for the preparation of 1-alkyl/aryl-5-alkylselanyl-1H-tetrazoles 96 and 99 from alkyl or arylisoselenocyanates 94 or 95 (Scheme 43). A one-pot protocol was used the preparation of 5-alkylselanyl-1-aryl-1H-tetrazoles 96 from the reaction of arylisoselenocyanates 94 with \(\hbox {NaN}_{3}\) and an alkylating agent. Also, N-alkyl-N-arylcyanamides 97 and (Z)-Se-alkyl-N-cyano-\(N\),\(N'\)-diarylisoselenoureas 98 were obtained as side products. When the alkylisoselenocyanates 95 were employed as the substrates, the reactions led to the formation of 1-alkyl-5-alkylselanyl-1H-tetrazoles 99 in moderate yields [77].
Synthesis of 1,5-DSTs containing a selanyl group
1,5-DSTs syntheses from amines
In 1957, 1-alkyl-substituted 5-nitroiminotetrazoles were prepared from the reaction of potassium methylnitramine with cyanogen bromide and \(\hbox {HN}_{3}\) [78]. In this process, methylnitrocyanamide 99 was first from the reaction of potassium methylnitramine with cyanogen bromide. Then, treatment of 99 with \(\hbox {HN}_{3}\) produced 1-methyl-5-nitroiminotetrazole 100 (Scheme 44).
Preparation of a 1-alkyl-substituted 5-nitroiminotetrazole
Recently, several commercially available amine [79] and hydrazine [80] compounds were reacted with three equiv. of cyanogen azide dissolved in acetonitrile/water solution (4:1) to afford to afford an array of imidoyl azide intermediates. Subsequent cyclization led to 1-substituted 5-aminotetrazoles 101. This procedure also was employed in the productions of bis- and tris(1-substituted 5-aminotetrazole) derivatives (Scheme 45). These aminotetrazoles were nitrated with 100 % nitric acid to produce mono-, di-, and trisubstituted nitroiminotetrazole derivatives [81].
A new combination of 1,1-difluoroazides 102 with different amines for the synthesis of fluorine-containing 1,5-DSTs 103 was described by Lermontov and co-workers [82] who found best conditions to be at room temperature in dry EtOH or THF. Although the reaction is sensitive to steric effect, two bulky adamantyl- and tert-alkyl-containing amines were successfully transformed into their corresponding tetrazoles where the 103:104 ratio was not dependent on the solvent. In the case of azide 102b, the expected amide was obtained using an excess amount of amine (Scheme 46).
Synthesis of 1-substituted 5-aminotetrazoles
Synthesis of fluorine-containing 1,5-DSTs
The synthesis of various fused 1,5-DSTs such as 6-aminotetrazolo[1,5-f][1,2,4]triazin- 8(5H)-one 106a [83], na-phtho[2,3- e]tetrazolo[5,1- c][1,2,4]triazine 106b [84], tetrazolo[l,5 -b][1,2,4]triazines 106c [85], 4,7- diphenylfuro[3,2 -e][1,2,3,4]tetraazolo[1,5- a]pyrimidine- 5(4H)-imine106d [86], ditetrazolo[1,5- b: \(1'\),\(5'\)- d][1,2,4]triazines 106e [87], and 106f [88] from the corresponding aryl hydrazines with nitrous acid \((\hbox {HNO}_{2})\) has been reported (Scheme 47).
Synthesis of fused 1,5-DSTs
1,5-DSTs syntheses from ketones
The reaction of TMS-\(\hbox {N}_{3}\) with different ketones was established to be an efficient process for the preparation of 1,5-DSTs in the presence of Lewis acid via Schmidt rearrangement [89]. Elmorsy and co-workers have shown that \(\hbox {SiCl}_{4}/\hbox {NaN}_{3}\) is an effective system for the direct transformation of ketones or \({\upalpha }\),\({\upbeta }\)-unsaturated ketones to 1,5-DSTs 107 in excellent yields (Scheme 48) [90]. Furthermore, ketones can be reacted with \(\hbox {HN}_{3}\) [91] or \(\hbox {NaN}_{3}\) [92] in the presence of a catalytic amount of \(\hbox {TiCl}_{4}\) to give 1,5-DSTs.
\(\hbox {SiCl}_{4}\)-catalyzed synthesis of 1,5-DSTs
Cristau et al. demonstrated a simple process for the regioselective preparation of 1,5-DSTs 108 from the reaction of \({\upbeta }\)-keto ester, TMS-\(\hbox {N}_{3}\) and \(\hbox {ZnBr}_{2}\) at 60 \(^{\circ }\hbox {C}\) under solvent-free conditions (Scheme 49) [93]. This protocol was also useful for the preparation of fused 1,5-DSTs using of seven-membered \(\beta \)-keto esters and \(\hbox {HN}_{3}\) in the presence of \(\hbox {BF}_{3}{\cdot }\hbox {OEt}_{2}\) [94].
Synthesis of 1,5-DSTs from the \({\upbeta }\)-keto esters
The reaction of 1,8-dioxo-octahydroxanthenes with silyl azides (in situ formed by the treatment of the \(\hbox {SiCl}_{4}\) with \(\hbox {NaN}_{3}\)) led to the formation of new substituted pyrano-bis[3,2-c]tetrazolo[1,5-a]azepines 109 in high yields (Scheme 50) [95].
Salama et al. have developed the regiospecific synthesis of 1,5-DSTs 110 derived from of dienones with \(\hbox {SiCl}_{4}/\hbox {NaN}_{3}\) in \(\hbox {CH}_{3}\hbox {CN}\) under mild conditions [96]. A variety of functional groups on the aromatic ring in the dienones gave 1,5-DSTs in good to excellent yields. In addition, annulated 1,5-DST structures 110g and 110h were produced via the reaction of monocyclic and benzo-fused cyclic ketones (Scheme 51).
Synthesis of pyrano-bis[3,2-c]tetrazolo[1,5-a]azepines
1,5-DSTs syntheses from alkenes
In 1966, Hassner et al. reported the \(\hbox {AgClO}_{4}\)-promoted reaction of alkenes, halogens (\(\hbox {Br}_{2}\) or \(\hbox {I}_{2}\)), nitriles, and \(\hbox {NaN}_{3}\) to produce 1,5-DSTs [97]. More recently, a metal triflate-catalyzed one-pot synthesis of 1,5-DSTs was discovered by Hajra et al. who described the reaction of alkenes, N-bromosuccinimide (NBS), nitriles, and TMS-\(\hbox {N}_{3}\) for the preparation of 1,5-DSTs 111 [98]. A shorter reaction time was needed when using \(\hbox {Zn(OTf)}_{2}\) as a catalyst. The combination of a variety of alkenes and nitriles generated 1,5-DSTs containing an additional bromo functionality on the alkyl group linked to the N1 position. The mechanism includes the initial formation of halonium ion V, which once opened by the \(\hbox {R}^{3}\)–CN and followed by the reaction of the produced nitrilium ion W with azide, gives tetrazole tetrazole 111 in racemic form (Scheme 52).
Synthesis of conjugated tetrazole derivatives
\(\hbox {Zn(OTf)}_{2}\)-catalyzed reaction for the synthesis of 1,5-DSTs
Recently, Srihari et al. reported a domino reaction involving Michael addition/click chemistry for the preparation of substituted 1,5-DSTs 113 from Baylis–Hillman acetates 112 [99]. Diverse Baylis–Hillman acetates with an ester moiety were examined with several aryl nitriles and TMS-\(\hbox {N}_{3}\) in the presence of TBAF as a catalyst to produce the corresponding 1,5-DSTs in good yields under solvent-free reaction conditions (Scheme 53).
1,5-DSTs syntheses via alkylation of 5-substituted tetrazoles
One of the methods for the preparation of 1,5-DSTs is the substitution of 5-substituted tetrazoles (5-STs) at the N-1 atom. However, this method often leads to a mixture of both 1,5- and 2,5-DSTs regioisomers. Both reaction temperature and the properties of the substituent at the 5-position could affect the ratio of isomers [19].
Various reactions have been reported on the alkylation of 5-STs in recent years. The treatment of 5-STs with alkyl halides in the presence of a base provided the corresponding 1,5- and 2,5-DST derivatives as mixtures in which the 2,5-DST isomers were the major products (Scheme 54). Different bases such as \(\hbox {Et}_{3}\hbox {N}\) [100–102], N,N-diisoproplyethylamine (DIPEA) [1], and \(\hbox {K}_{2}\hbox {CO}_{3}\) [103] have been used.
Moreover, the alkylation of 5-STs under microwave irradiation conditions was also successful. Significant advantages of this method are shorter reaction times and higher yields in comparison with conventional heating conditions [104, 105].
Preparation of 1,5-DSTs from Baylis–Hillman acetates
Alkylation of 5-STs
The alkylation of 5-aryltetrazoles with dimethyl sulfate \((\hbox {Me}_{2}\hbox {SO}_{4})\) in \(\hbox {CHCl}_{3}\) under microwave irradiation conditions formed isomeric 1- and 2-methyl-5-aryltetrazoles (Scheme 55). The ratio of isomeric tetrazoles was established from the \(^{1}\hbox {H}\) NMR spectra where the chemical shifts of the methyl protons in the spectra of 1- and 2-methyl-5-aryltetrazoles are considerably different [106]. Also, the treatment of 5-STs with \(\hbox {CH}_{2}\hbox {N}_{2}\) leads to 1- and 2-methyl-5-ST isomers [107].
Methylation of 5-aryltetrazoles
The reaction of 5-STs with 1-[2-(2,4-difluorophenyl)-oxiranylmethyl]-1H-[1,2,4]-triazole afforded a mixture of 1,5- and 2,5-DSTs (Scheme 56). 2,5-DST isomers are the major products, despite the fact that steric factors show an important role in formation of regioisomers. These compounds revealed strong growth inhibitory activity against Candida spp. [108].
Synthesis of 1,5- and 2,5-DSTs
Acylation of 5-STs with N,N-dimethylcarbamoyl chloride offered a 0.58:1 mixture of 1,5- and 2,5-DST regioisomers which could be separated by silica gel chromatography (Scheme 57). These structures acted as inhibitors of cannabinoid inactivation. In addition, they have provided new SAR data for their interaction with the putative amide membrane transporter [109, 110].
Koldobskii and co-workers described the arylation of 5-aryl(alkyl)tetrazoles with 4-nitrofluorobenzene in the presence of NaOH in DMSO under microwave irradiation conditions (Scheme 58) [111].
The 5-aminotetrazole with both endocyclic nitrogen and exocyclic amino group contributed in the preparation of the fused 1,5-DSTs. The cyclocondensation reaction of 5-amino-tetrazole with \({\upalpha }\),\({\upbeta }\)-unsaturated carbonyl frameworks [112, 113], such as chalcones, Mannich bases, or arylidenepyruvic acids, led to formation of the tetrazolopyrimidines 123 and 124. Although the three-component reaction of 5-aminotetrazole with structurally diverse aromatic aldehydes and building blocks with activated methylene groups such as pyruvic acid, acetophenones, ethyl acetoacetate, and dimedone catalyzed by stoichiometric amounts of protic acid [114–118] as well as iodine [119] were investigated for the synthesis of tetrazolopyrimidines (Scheme 59).
The halocyclization of olefin-functionalised tetrazoles was described for the synthesis of fused 1,5-DST derivatives (Scheme 60). The reaction of olefin substituted tetrazoles with iodine [120] or bromine [121] in \(\hbox {NaH}\hbox {CO}_{3}/\hbox {CH}_{3}\hbox {CN}\) solution afforded fused 1,5-DSTs 126 and 127 in moderate to excellent yields.
Acylation of 5-STs
Arylation of 5-STs
Synthesis of tetrazolopyrimidines
Halocyclization of olefin-functionalised tetrazoles
The preparation of tetrazolo-sugars 128 via sequential reaction involved the fragmentation of anomeric alkoxyl radicals (ARF) and then an intramolecular cyclization promoted by hypervalent iodine reagents [122]. The ARF reaction of the hemiacetals was done in dry ethyl acetate by treatment with iodosylbenzene and iodine under refluxing and irradiation with of two tungsten lamps. A number of five- to seven-membered ring fused tetrazoles were obtained (Scheme 61).
The synthesis of fused 1,5-DST derivatives via three-component reaction between an aldehyde, an isocyanide, and proline tetrazole was described by Ley and co-workers [123]. This reaction can be regarded as an Ugi-type four-center/three-component coupling reaction (U-4C/3-CCR) in which the tetrazole and pyrrolidine components act as the tethered bifunctional amine/acid component to react with the aldehyde and isocyanide components. A plausible mechanism of the U-4C/3-CCR involves the formation of iminium ion X followed by the nucleophilic addition of the isocyanide to give intermediate Y, which upon intramolecular cyclization afforded the final product 129 (Scheme 62). A variety of isocyanides and aldehydes were effectively examined in this reaction.
1,5-DSTs syntheses via coupling of 1-substituted tetrazoles
The Suzuki–Miyaura coupling reaction of 1-substituted-5-halotetrazole with various functionalized arylboronic acids were used for the syntheses of 1,5-DSTs. The cross-coupling reaction of 1-substituted-5-bromotetrazole with aryl boronic acids in the presence of 3 mol% \(\hbox {Pd(PPh}_{3})_{4}\) and 2 equiv of \(\hbox {K}_{2}\hbox {CO}_{3}\) [124] or \(\hbox {Na}_{2}\hbox {CO}_{3}\) [125] in refluxing toluene was described. Under these conditions, the corresponding 1,5-DSTs were achieved with 23–97 % yields as one regioisomer (Scheme 63). Moreover, Suzuki–Miyaura coupling reactions of 1-substituted-5-chlorotetrazole with different substituted arylboronic acids were studied [126–128]. In the presence of a catalytic amount of 2- dicyclohexylphosphino -\(2',6'\) -dimethoxybiphenyl \(\hbox {(SPh} \hbox {os)/Pd(OAc)}_{2}\), 1,5-diaryltetrazoles were obtained in good yields. Only one example of Pd-catalyzed cross-coupling of organozinc reagent with 1-substituted-5-chlorotetrazole (Negishi coupling) has been reported for the preparation of 1,5-DST [129].
Synthesis of tetrazolo-sugars
Three-component coupling process for the synthesis of fused 1,5-DSTs
Suzuki–Miyaura coupling reaction for the synthesis of 1,5-DSTs
A simple and an effective reaction was established for the synthesis of 1-alkyl-5-(dialkylamino)tetrazoles 131 by Grygorenko and co-workers (Scheme 64) [130]. In this approach, nucleophilic substitution in 1-alkyl-5-sulfonyltetrazoles with anions (produced from the primary or secondary amines) results in the formation of 1,5-DSTs. In general, the reaction of 1-substituted-5-bromotetrazoles with amines provided desired 1,5-DSTs in good yields [58, 131].
Direct C–H arylation and alkenylation of 1-substituted tetrazoles was done via Pd catalysis in the presence of CuI and \(\hbox {Cs}_{2}\hbox {CO}_{3}\) [132]. The process requires the use of a phosphine ligand such as tris(2-furyl)phoshine (TFP) to avoid the intermediate tetrazolyl-\(\hbox {Pd}^{\mathrm{II}}\) species from fragmentation into the corresponding cyanamide (Scheme 65). In this work, diverse 1,5-DSTs were synthesized in good to excellent yields.
Another protocol used for the C–H alkenylation of 1-substituted tetrazoles [133, 134] involves the sequential lithiation of the tetrazole C5 position with n-butyllithium at \(-90\,^{\circ }\hbox {C}\), and then followed by the addition of a ketone to provide product 133 in 63 % yield (Scheme 66).
The Pictet–Spengler reaction was used for the preparation of fused 1,5-DST derivatives 135 [135]. To facilitate endo cyclization, the substrates were designed by employing the concept of an aryl amine linked to a deactivated heteroaromatic ring. So, the Pictet–Spengler condensation reaction of 2-tetrazol-1-yl-phenylamine 134 with aldehydes led to the preparation of new fused 1,5-DSTs (Scheme 67). Aldehydes with strong electron-donating groups such as N,N-dimethylbenzaldehyde did not react as expected with substrate 134 likely because the deactivated \(\uppi \)-nucleophile system was unsuccessful to enable C–C bond formation.
Nucleophilic substitution in 1-alkyl-5-sulfonyltetrazoles
Pd-catalyzed synthesis of 1,5-DSTs
Synthetic route towards 1,5-DSTs
Pictet–Spengler reaction for the preparation of fused 1,5-DSTs
Miscellaneous
1,5-DSTs were efficiently constructed by two C(sp3)–H and one C–C bond cleavages under mild and neutral reaction conditions [136]. The reaction of 1,3-diphenylprop-1-enes 136 with TMS-\(\hbox {N}_{3}\) in the presence of DDQ and CuI afforded 1,5-DSTs 137 (Scheme 68). The rearrangement of this reaction found that the aryl groups have a better migratory ability to the nitrogen atom than alkenyl groups. Remarkably, in these reaction conditions, bis-arylmethanes could also be effectively transformed into the corresponding 1,5-diaryl tetrazoles in 32–65 % yields.
Direct transformation of 1,3-diarylprop-1-enes to 1,5-DSTs
The reaction of trifluoromethylazoalkanes 138 with \(\hbox {NaN}_{3}\) produced 5-azidotetrazoles 139 in 49–99 % yields (Scheme 69). This reaction occurred when alkyl groups of 138 have a hydrogen atom at their \(\alpha \)-carbon. For example, with groups such as tert-butyl or phenyl, the reaction did not occur even under vigorous reaction conditions [137].
Synthesis of 5-azidotetrazoles
A process for the synthesis of tetrazolo[1,5-a]pyridines 140 from 2-halopyridines has been developed by utilizing TMS-\(\hbox {N}_{3}\) in the presence of tetrabutylammonium fluoride hydrate (\(\hbox {TBAF}{\cdot }\hbox {xH}_{2}\hbox {O}\)) (Scheme 70) [138]. The reaction of 2-halopyridines with 2-chloroquinoline and 1-chloroisoquinoline provided tetrazolo[1,5-a]quinoline and tetrazolo[5,1-a]isoquinoline, respectively.
Preparation of tetrazolo[1,5-a]pyridines
Conclusions
Tetrazoles are nitrogen-rich heterocyclic structures that possess a wide range of chemical, and biological and medicinal applications. Recently, the synthesis of 1,5-DSTs has been of great interest in the literature. In this review, we have classified numerous described processes for the synthesis of 1,5-DSTs with most of them being reported in recent years. We hope this review will be of great interest for the general readership of this journal.
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The authors gratefully acknowledge the partial support from the Research Councils of the Iran University of Science and Technology and Babol University of Technology.
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Sarvary, A., Maleki, A. A review of syntheses of 1,5-disubstituted tetrazole derivatives. Mol Divers 19, 189–212 (2015). https://doi.org/10.1007/s11030-014-9553-3
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DOI: https://doi.org/10.1007/s11030-014-9553-3