Synthesis of six-membered cyclic carbamates employing CO2 as building block: A review

Journal of CO₂ Utilization 33 (2019) 37–45

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Synthesis of six-membered cyclic carbamates employing CO2 as building block: A review

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Xue Zhaoa,b, , Shihai Yangb, Saeideh Ebrahimiaslc,d, Sattar Arshadie, Akram Hosseinianf a

School of Biological and Pharmaceutical Engineering, Jilin Agricultural Science and Technology University, Jilin, 132101, China School of Traditional Chinese Medicine, Jilin Agricultural University, Changchun, 130118, China c Department of Chemistry, Ahar Branch, Islamic Azad University, Ahar, Iran d Industrial Nanotechnology Research Center, Tabriz Branch, Islamic Azad University, Tabriz, Iran e Department of Chemistry, Payame Noor University, Tehran, Iran f School of Engineering Science, College of Engineering, University of Tehran, P.O. Box 11365-4563, Tehran, Iran b

A R T I C LE I N FO

A B S T R A C T

Keywords: CO2 Six-Membered cyclic carbamates Carboxylative cyclization Dehydrative condensation γ-Amino alcohols

The utilization of carbon dioxide (CO2) as a sustainable and renewable one-carbon (C1) building block in organic synthesis has attracted great attention since it may provide access to profitable chemicals from an abundant, non-toxic, non-flammable and inexpensive resource. Among these transformations, synthesis of biologically and synthetically important six-membered cyclic carbamates employing CO2 as building block represents one of the hottest and attractive research topics in the field. This focus-review survey the available literature on the synthesis of titled compounds from the reaction of various substrates (e.g., γ-amino alcohols, γ-haloamines, homoallylic amines, propargylic amines, o-alkynylanilines) with CO2, by hoping that it will encourage researchers to further thinking and research in this explosively growing field.

1. Introduction Six-membered cyclic carbamates (1,3-oxazinan-2-ones) are the ubiquitous structural core of many natural products, pharmaceuticals, and drug-like molecules [1]. For example (Fig. 1), Maytansine 1 is a 19membered ring ansa-macrolide structure attached to a 1,3-oxazinan-2one ring which was first isolated in 1972 from the East African shrubs Maytenus serrata [2]. This plant alkaloid has high tubulin-binding affinity and potent inhibitory activities against many tumor cell lines [3]. Efavirenz 2 with brand name of Sustiva is a synthetic oxazinan-2-one antiretroviral medication marketed worldwide for the treatment and prevention of the human immunodeficiency viruses (HIV) [4]. Droxicam 3 is a non-steroidal anti-inflammatory drug which is a pro-drug of piroxicam [5]. The drug used for the relief of pain and inflammation in musculoskeletal disorders. 1,3-Oxazinan-2-ones are also versatile synthetic precursors in the construction of different organic substrates, such as piperidine-2,4-diones [6], β-amino-aldehydes [7], β-lactams [8], and 1,3-oxazinane-2-thiones [9] as shown by the high number of papers reported in the literature. Furthermore, these compounds have also been used as chiral auxiliaries in asymmetric syntheses [10]. Due to wide importance of 1,3-oxazinan-2-one cores in medicinal chemistry and organic synthesis, many strategies have been developed to achieve

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these compounds [11]. However, most of the classical methods for the preparation of the titled compounds limited by requiring highly toxic starting materials (e.g., phosgene, isocyanate derivatives), forcing reactions conditions, or not easily accessible starting materials. Recently, cyclization reaction of amines with dialkyl carbonates has attracted a lot of attentions from synthetic chemists as an efficient and straightforward synthetic route to 1,3-oxazinan-2-ones [12]. However, the scope of commercially available dialkyl carbonates are narrow and the requirement of substrates pre-functionalization limits the synthetic utility of this method. Therefore, there is still further need to develop novel and practical methods for the synthesis of titled compounds from simple and easily accessible starting materials. Due to environmental concerns for global warming and ocean acidification, the development of efficient and practical methods to transform CO2, a naturally abundant, nonflammable, nontoxic, and renewable C-1 feedstock, into profitable chemicals has attracted more attention over the years [13–16]. However, CO2 is highly stable (ΔG°∼−394 kJ/mol) and its ultra-low reactivity is a clear challenge to develop truly efficient chemical transformations [17,18]. Despite inert nature and thermodynamic stability of CO2, a variety of catalytic systems has been recently developed that effectively promote the incorporation of this molecule into value added chemicals such as

Corresponding author at: School of Biological and Pharmaceutical Engineering, Jilin Agricultural Science and Technology University, Jilin, 132101, China. E-mail address: [email protected] (X. Zhao).

https://doi.org/10.1016/j.jcou.2019.05.004 Received 25 February 2019; Received in revised form 26 April 2019; Accepted 1 May 2019 2212-9820/ © 2019 Elsevier Ltd. All rights reserved.

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Fig. 1. Selected examples of some bioactive six-membered cyclic carbamate derivatives.

Fig. 2. Conversion of CO2 into six-membered cyclic carbamates.

Scheme 1. (a) Munoz's synthesis of 2,5-disubstituted 2-oxazinone 7; (b) carbonylative cyclization of 2-aminomethylphenols 9 with CO2 developed by Munoz.

various substrates in the presence of CO2 (Fig. 2), with the emphasis on the mechanistic features of the reactions. The dehydrative condensation of γ-amino alcohols with CO2 are discussed first. This is followed by carboxylative cyclization of homoallylic/propargylic amines with CO2 and cyclization of γ-haloamines with CO2. Finally, the cyclization of 2alkynylanilines with CO2 will be covered at the end of the review.

quinazoline-2,4(1H,3H)-diones [19], azoles [20], 2-alkynoates [21], urethanes [22], and carbonates [23]. Among these transformations, synthesis of 1,3-oxazinan-2-one derivatives employing CO2 as building block have undergone an explosive growth over the past few years. To the best of our knowledge, a comprehensive review has not appeared on the synthesis of these heterocycles using CO2 in literature thus far. As a part of our continuing reviews on chemical fixation of CO2 into useful products [19–24] and new methodologies in organic synthesis [25], in this focus-review we will highlight the most important and influential breakthroughs in the synthesis of 1,3-oxazinan-2-one derivatives using

2. From amino alcohols Construction of 1,3-oxazinan-2-one cores through the dehydrative 38

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Scheme 6. Fixation of atmospheric CO2 with homoallylic amines 16 in the presence of molecular iodine.

Scheme 2. Synthesis of 1,3-oxazinan-2-one 11 form 3-aminopropanol 10 and CO2.

tetramethyl-2-phenylguanidine (PhTMG) and diphenylphosphoryl azide (DPPA) under CO2 atmosphere in MeCN, resulted in carbamoyl azide 5 in 63% yield together with a trace of phosphorylated carbamoyl azide 6. They described that carbamoyl azide 5 underwent an intramolecular cyclization reaction when treated with NaH as a base in THF, giving 2,5-disubstituted 2-oxazinone 7 in almost quantitative yield (Scheme 1a). Interestingly, when the reaction was performed with acetyl chloride as the activating agent, the expected product 7 was obtained in 96% yield in a single step. The authors also found that the 2-aminomethylphenol derivatives 8 were directly converted to the corresponding 3,4-dihydrobenzo[e][1,3]oxazin-2-ones 9, via carbonylative cyclization using PhTMG as a base and DPPA as an activating agent (Scheme 1b). It is important to point out that the conformational rigidity as well as the higher acidity of the phenol moiety contribute to the successful carbonylation with DPPA. In the same year, Corma and García along with their co-workers found that simple 3-aminopropanol 10 can undergo a ceria (CeO2) catalyzed coupling with CO2 (7 atm) at 160 °C to afford unsubstituted 1,3-oxazinan-2-one 11, although in only 23.7% yield (Scheme 2) [27]. Interestingly, when the same reaction was performed in the absence of any catalyst and additive at slightly higher pressure of CO2 (10 atm) and higher temperature (180 °C), the expected product was obtained in 24.3% yield [28]. In 2013, Tomishige and colleagues reported the preparation of a series of 1,3-oxazinan-2-ones 13 in quantitative yields via CeO2-catalyzed carbonylative cyclization of γ-amino alcohols 12 with CO2 in acetonitrile (Scheme 3) [29,30]. Of note, this CO2 fixing reaction is equally efficient for both primary and secondary amines. However, high pressure of CO2 (50 atm) was required to drive the transformation. Based on a series of kinetics and FTIR studies, the authors speculated that this CeO2-catalyzed reaction comprises the following basic steps (Scheme 4): (i) formation of carbonate (OeCOeO) and carbamate (OeCOeN) adspecies of amino alcohol on CeO2 from starting γ-amino alcohol 12 and CO2; (ii) decomposition of the carbonate adspecies to the hydroxyl group and CO2; (iii) intramolecular nucleophilic addition of the OH group to the carbamate adspecies on CeO2, providing a 1,3oxazinan-2-one coordinated ceria complex; and (iv) desorption of 1,3oxazinan-2-one and regeneration of CeO2. Very recently, the group of Fernández-Repo described an efficient dehydrative condensation of γ-amino alcohols 14 with CO2 employing p-toluenesulfonyl chloride (TsCl) as a hydroxyl group activating reagent and Cs2CO3 as a base (Scheme 5) [31]. This CO2 fixation reaction afforded the optimum yield in acetone at room temperature. Various aliphatic and aromatic amino alcohols were used to establish the general applicability of the method. It is to be noted that under optimized conditions β-amino alcohols were also converted to the corresponding 2-oxazolidinones in moderate to high yields.

Scheme 3. CeO2-catalyzed carbonylative cyclization of γ-amino alcohols 12 with pressurized CO2.

Scheme 4. Proposed mechanism for the reaction in Scheme 3.

Scheme 5. Synthesis of 1,3-oxazinan-2-ones 15 reported by Repo.

condensation of corresponding γ-amino alcohols with CO2 is probably the area that has experienced the highest average growth in the field over the past few years. One of the earliest reports on this chemistry was published by Munoz and co-workers in 2010 [26], who showed that the treatment of 3-amino-2,2-dimethylpropanol 4 with 1,1,3,3-

3. From homoallyl amines Although direct synthesis of five-membered cyclic carbamates via chemical fixation of CO2 to allylic amines has been well known [24e], the carboxylative cyclization of homoallylic amines with CO2 into 39

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Scheme 7. Three component reaction between homoallylic amines 18, CO2 and tBuOI.

Scheme 8. Johnston's synthesis of chiral 1,3-oxazinan-2-ones 22.

Scheme 9. Pd-catalyzed carboxylative cyclization of homopropargylic amines 23 with atmospheric CO2.

iodine as an electrophilic source in MeOH to form the corresponding 1,3-oxazinan-2-ones 17 under mild and catalyst-free conditions (Scheme 6) [32]. Later, Muñoz and co-workers significantly improved the efficiency of this reaction using 2-phenyl-1,1,3,3-tetramethylguanidine (PhTMG) as a non-nucleophilic base in acetonitrile

corresponding six-membered cyclic carbamates was less developed. The first report of the 1,3-oxazinan-2-one core synthesis through carboxylative cyclization of homoallylic amines with CO2 has been reported by Toda and Kitagawa in 1987, when homoallylamines 16 underwent cyclizative coupling with CO2 in the presence of 50 mol% of molecular 40

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expected product 19 (Scheme 7b). Very recently, the group of Johnston described the use of methoxyquinolinederived bifunctional bis(amidine)−triflimidic acid complex 20 as a chiral organocatalyst for enantioselective synthesis of sixmembered cyclic carbamates 22 via a three-component reaction between secondary homoallylic amines 21, CO2 and N-iodosuccinimide (Scheme 8) [35]. The reactions were carried out in wet toluene (90 ppm water) at −20 °C, tolerated various functional groups, and provided 1,3-oxazinan-2-one products 22 in moderate to high yields (55–85%) with modest to excellent levels of chiral induction (40–95% ee). However, this protocol for cyclization of unsubstituted homoallylamines was considerably less efficient. The authors speculated that this organocatalyzed CO2-fixation reaction proceeds along the similar mechanistic pathway that described in Scheme 7b, and dual Brønsted acid/base catalysis stabilizes the carbamic acid intermediate through the hydrogen bond donor-acceptor interaction and creates a chiral environment during the carbon–oxygen bond formation step.

Scheme 10. Synthesis of functionalized 1,3-oxazinan-2-ones 26 via Ag-catalyzed fixation of CO2 with homopropargylic amines 25.

4. From homopropargylic amines The synthesis of five membered cyclic carbamates by cyclization of propargylic amines with CO2 has attracted much attention in recent years as we highlighted in our recent review [24a]. However, very little attention has been focusing on the carboxylative cyclization of homopropargylic amine with CO2. In 2017, Vaca and Bourissou along with their colleagues realized the first indenediide-based Pd SCS pincer complex catalyzed CO2 fixation with homopropargylic amines 23, providing an interesting and novel approach for the synthesis of 1,3oxazinan-2-one derivatives 24 under mild reaction conditions (Scheme 9) [36]. However, the protocol required long reaction times and generated the final products in unsatisfactory yields. Soon after, Liu-Li's research team demonstrated that the combination of AgOAc with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) could serve as an efficient catalytic system for the carboxylative cyclization of terminal homopropargylic amines 25 with CO2 under solvent-free conditions, leading to formation of various functionalized 1,3-oxazinan2-one derivatives 26 in excellent to quantitative yields (Scheme 10) [37]. Beside excellent yields, broad substrate scope, and easy scalability were other advantages of this CO2-fixation reaction. It is important to note that other metal catalysts [e.g., ZnCl2, FeCl3, CuCl2, Mn(OAc)2] were also found to promote the cyclization, albeit in lower yields. The authors showed that the exocyclic C]C bonds of products could be rearranged to intra-cyclic olefin with excellent yields by heating (130 °C) in the presence of PPh3AuCl/AgOTf/PTSA system in DCM. The mechanism proposed by the authors for this carboxylative cyclization reaction is shown in Scheme 11. The initial activation of homopropargylic amine 25 by DBU affords the intermediate A, which subsequently reacts with CO2 to give the carbamic salt B. Next, intramolecular 6-exo-oxygen-cyclization of intermediate B furnishes the species C, which after protonation–demetallation affords the expected product 26 and regenerates the Ag+ and DBU.

Scheme 11. Mechanism that accounts for the formation of 1,3-oxazinan-2-one derivatives 26.

Scheme 12. Synthesis of unsubstituted 1,3-oxazinan-2-one 11 via KOH-mediated cyclization of γ-haloamines 27 with CO2.

[33]. However, only one example was reported. In 2012, Minakata and colleagues smartly used tert-butyl hypoiodite (tBuOI) as an iodinating reagent in the carboxylative cyclization of homoallylamines with atmospheric CO2 [34]. Thus, in the presence of stoichiometric amount of tBuOI in acetonitrile at -20 °C, fixation of CO2 (1 atm) with primary homoallylamines 18 furnished the corresponding 1,3-oxazinan-2-ones 19 in moderate yields (Scheme 7a). Of note, allylamines and propargyl amines were also suitable substrates in the process, providing corresponding five-membered carbamates in good to excellent yields. A mechanism that explains this cyclization reaction starts with the formation of homoallyl carbamic acid intermediate A by reaction of homoallylamine 18 with CO2. Its proton-iodine exchange with tBuOI leads to O-iodinated species B that converts to cyclic iodonium intermediate C through an intramolecular iodination process. Finally, intramolecular cyclization of intermediate C leads to the

5. From γ-haloamines Synthesis of six-membered cyclic carbamates through cyclization of γ-haloamines with CO2 has been scarcely studied, to the best of our awareness, only three examples of such a transformation were reported in the literature till now. In 2014, Repo and co-workers realized the carboxylative cyclization of γ-haloamines 27 with CO2 (35 atm) in the presence of a base and in the absence of catalyst [38]. After screening different bases (e.g., K2CO3, KOH, Et3N), and solvents (e.g., H2O, MeCN, EtOH), KOH and EtOH were proven to be the most effective base and solvent, respectively, for the reaction. Using the optimized conditions, the target 1,3-oxazinan-2-one 11 were isolated in excellent yields (Scheme 12). Notably, β-haloamines were also suitable substrates in the process, providing corresponding five-membered cyclic carbamates in 41

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Scheme 13. Three-component fixation of atmospheric CO2 with aromatic amines 28 and 1,3-dibromopropane 29.

Scheme 14. Shi's synthesis of N-substituted 1,3-oxazinan-2-ones 33.

Scheme 15. Mechanism of the [Bmim]OAc-catalyzed synthesis of 3-aryl-1,3-oxazinan-2-ones 33.

Scheme 16. Yamada's synthesis of benzoxazine-2-one derivatives 35.

almost quantitative yields. Interestingly, when a β,γ-dihaloamine (2,3dichloroamine) was used as substrate under the standard condition, a mixture of five- and six-membered-ring carbamates were formed with preference for five-membered product. The use of longer reaction times

led to higher conversions but almost did not improve the selectivity of the reaction. DFT calculations also suggested that five-membered carbamate is more stable than six-membered carbamate. Shortly afterwards, the same authors disclosed a one-pot, three42

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Scheme 17. Proposed mechanism for Ag-catalyzed incorporation of CO2 into 2-alkynylanilines 35. Scheme 18. Three-component reaction between 2-(1-haloalkyl)-oxiranes 36, aliphatic primary amines 37, and CO2.

2-ones 33 was successfully produced by treatment of corresponding aromatic amines 31 with 1,3-dichloropropane 32 under a CO2 (1 atm) atmosphere (Scheme 14). Just like Repo's work, five- and seven-membered cyclic carbamates could also effectively synthesized employing 1,2-dichloroethane and 1,4-dichlorobutane as the electrophiles upon the optimized conditions. However, 1,5-dichloropentane, 1,6-dichlorohexane and 1,10-dichlorodecane failed to enter into this cyclization reaction and only corresponding acyclic linear carbamate was obtained. The mechanism proposed by the authors for this reaction is illustrated in Scheme 15. Scheme 19. Suggested mechanism for the reaction in Scheme 18.

6. From 2-alkynylaniline component version of above-mentioned reaction where the requisite γhaloamines were prepared in situ from 1,3-dibromopropane and primary amines [39]. Thus, the reaction between aromatic amines 28, 1,3dibromopropane 29 and atmospheric CO2 in the presence of 2-tBuTMG/ Cs2CO3 combination as a catalytic system in MeCN afforded N-substituted 1,3-oxazinan-2-one derivatives 30 in moderate to high yields (Scheme 13). Various functional groups are tolerated by the reaction conditions employed, that may provide an opportunity for further manipulation of products. Furthermore, the protocol was applicable for the preparation of synthetically challenging seven-membered carbamates. A modification of this six-membered urethane synthesis was reported by Shi and colleagues, who reported that the optimal conditions involve the use of [Bmim]OAc/Bu4NBr/Cs2CO3 system at 90 °C [40]. Under the optimized conditions a library of N-substituted 1,3-oxazinan-

In 2013, the group of Yamada achieved the synthesis of biologically important 1H-benzo[d][1,3]oxazin-2(4H)-ones 35 from N-substituted 2-alkynylanilines 34 and carbon dioxide catalyzed by a AgNO3 and DBU system under 10 atm CO2 pressure at 20 °C using DMSO as the solvent (Scheme 16) [41,42]. The expected benzoxazine-2-one derivatives 35 were obtained with yield ranging from 85% to 99% within 24 h under the optimized reaction conditions. Of note, benzoxazine-2-ones containing (Z)-exo-olefin have been isolated in all cases as the sole products. Primary anilines also produced the corresponding products smoothly. In these cases, the use of 10 mol% of AgOAc and 2 equiv. of DABCO (1,4-diazabicyclo[2.2.2]octane) gave the best results. The present catalytic system was also catalyzed the carboxylative cyclization of unsubstituted terminal 2-alkynylaniline; however, in insufficient yield. The yield of this reaction was improved to 75% when catalyzed by silver(II) picolinate instead of AgOAc. It should be mentioned that the Scheme 20. Al-catalyzed coupling of oxetane 42 with CO2.

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References

presence of silver salts were crucial for this interesting CO2 incorporation reaction, since other metal salts such as Pd, Pt, Rh, Au, and Cu were completely unable to catalyze this reaction. Later, a contribution from the group of Finashina demonstrated the combination of a heterogeneous Ag-containing catalysis [Ag(1%)-γ-Al2O3(F)] and Cs2CO3 to facilitate similar reactions [43]. The mechanism of this CO2-fixation reaction was proposed based on DFT calculations, determining that the reaction starts with the formation of an Ag-alkynylaniline-DBU complex A by coordination of Ag to the carbon-carbon triple bond of 2-alkynylaniline 34, and simultaneously formation of a hydrogen bond between amino group of 2-alkynylaniline 34 and DBU. Next, trapping of CO2 by activated amino group of complex A affords an Ag-alkynylaniline−CO2 complex B, which after an intramolecular 5-exo-dig cyclization leads to the intermediate C. Finally, the proto-demetallation of C through intermediate D provides the final product 35 (Scheme 17) [44].

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7. Miscellaneous reactions In 1993, Yoshida, Ohshima, and Toda reported an efficient catalystand additive-free three-component coupling with 2-(1-haloalkyl)-oxiranes 36, aliphatic primary amines 37, and CO2 to prepare six-membered cyclic carbamates 38 bearing a hydroxyl group at the C5-position (Scheme 18) [45]. The reaction were performed in MeOH at room temperature and gave the expected carbamates with yield ranging from 21% to 77%. Interestingly, when the same reaction was carried out in the presence of a base, the corresponding five-membered carbamates 39 were formed instead. A proposed mechanism for this reaction is depicted in Scheme 19. In 2015, the group of Kleij reported an example of 1,3-oxazinan-2one synthesis through the coupling of oxetane and CO2 [46]. They showed that in the presence of 2.5 mol% of Al catalyst 40 and 5.0 mol% of TBAB, oxetane 41 underwent ring-opening and a subsequent CO2 insertion and ring-closing to afford six-membered carbamate 42 in 84% yield (Scheme 20).

8. Conclusion Since CO2 was utilized as an economical, abundant, non-flammable and environmental friendly C1 source to the synthesis of carbamate derivatives, a large number of excellent reviews on the synthesis of acyclic and five-membered cyclic carbamates employing CO2 as building block were published in recent years. However, no review has been appeared on the synthesis of six-membered cyclic carbamates using CO2 as the carbon source in literature thus far. This focus-review is the first of its kind to collect literature on the conversion of CO2 into biologically and synthetically important six-membered cyclic carbamates. As illustrated, a range of functionalized 1,3-oxazinan-2-ones could be easily achieved by fixation of CO2 into various substrates such as γ-amino alcohols, γ-haloamines, homoallylic amines, propargylic amines, o-alkynylanilines indicating the versatility of this page of sixmembered cyclic carbamate synthesis. Although all of the reactions covered in this review employ CO2 as a sustainable C1 feedstock, in some cases the reaction conditions are not very green. This is evident when reagents include acyl chloride, p-toluensulfonyl chloride, γ-haloamines, DMSO, etc. We hope this review will stimulate researchers to develop more environmentally friendly synthetic access routes to 1,3oxazinan-2-one cores based on the use of CO2. Acknowledgement This investigation has been supported by Key Construction Disciplines of Biology, Jilin College of Agricultural Science and Technology. 44

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