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Molybdenum‐Catalyzed Deoxygenative Cyclopropanation of 1,2

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Molybdenum‐Catalyzed Deoxygenative Cyclopropanation of 1,2 Angewandte Communications Chemie How to cite: Deoxygenative Cyclopropanation International Edition: doi.org/10.1002/anie.202103429 German Edition: doi.org/10.1002/ange.202103429 Molybdenum-Catalyzed Deoxygenative Cyclopropanation of 1,2-Dicarbonyl or Monocarbonyl Compounds Li-Ya Cao, Jian-Nan Luo, Jia-Sheng Yao, De-Ku Wang, Yuan-Qing Dong, Chao Zheng, and Chun-Xiang Zhuo* Abstract: The transition-metal-catalyzed cyclopropanation of in these processes.[6] Unfortunately, the highly energetic diazo alkenes by the decomposition of diazo compounds is a power- compounds are potentially explosive. In addition, hazardous ful and straightforward strategy to produce cyclopropanes, but reagents and multiple synthetic steps are often required for is tempered by the potentially explosive nature of diazo the preparation of the diazo substrates.[4, 7] Therefore, devel- substrates. Herein we report the Mo-catalyzed regiospecific oping operationally safe and readily available alternatives to deoxygenative cyclopropanation of readily available and the diazo carbonyl compounds as carbene precursors would bench-stable 1,2-dicarbonyl compounds, in which one of the benefit synthetic applications, especially for industrial-scale two carbonyl groups acts as a carbene equivalent upon synthesis.[8,9] deoxygenation and engages in the subsequent cyclopropana- 1,2-Dicarbonyl compounds are readily available and often tion process. The use of a commercially available Mo catalyst serve as valuable building blocks in organic synthesis.[10] afforded an array of valuable cyclopropanes with exclusive Specifically, these bench-stable compounds may be used to regioselectivity in up to 90% yield. The synthetic utility of this prepare the a-diazo carbonyl compounds.[7] Accordingly, we method was further demonstrated by gram-scale syntheses, questioned whether the 1,2-dicarbonyl compounds could be late-stage functionalization, and the cyclopropanation of utilized directly as carbene equivalents through transition- a simple monocarbonyl compound. Preliminary mechanistic metal-catalyzed regioselective deoxygenation for the syn- studies suggest that phosphine (or silane) acts as both a mild thesis of cyclopropanes, thus avoiding the tedious preparation reductant and a good oxygen acceptor that efficiently regen- and use of hazardous diazo compounds (Scheme 1B). erates the catalytically active Mo catalyst through reduction of Although conceptually simple in design, several fundamental the Mo-oxo complexes. requirements need to be met to achieve such a transition- metal-catalyzed regioselective deoxygenative cyclopropana- As a unique and important structure motif, the cyclopropane tion reaction. Specifically, a powerful transition-metal catalyst ring is widely found in many biologically active natural has to be identified that is capable of promoting a regiose- products and pharmaceuticals,[1,2] such as mitrephor- lective deoxygenation of a 1,2-dicarbonyl compound and one A,[2a,b] ingenol,[2c,d] duocarmycin A,[2e,f] saxagliptin,[2g] and inhibiting side reactions such as dimerization and competitive beclabuvir[2h] (Figure 1). To this end, numerous efforts have CÀH bond insertion when allylic substrates are applied. In been devoted to the synthesis of functionalized cyclopro- addition, a mild reductant and an oxygen acceptor should be panes.[3] Among the various synthetic strategies for the realized that will not directly reduce the 1,2-dicarbonyl group, generation of these unique carbocycles, the cyclopropanation but could efficiently regenerate the catalytically active of alkenes with transition-metal carbene species is powerful transition-metal catalyst through reduction of the metal-oxo and straightforward (Scheme 1A).[4,5] Metal carbene species, complexes. Furthermore, the generation of carbene equiva- usually generated in situ through the decomposition of a- lents through a transition-metal-catalyzed regioselective diazo carbonyl compounds promoted by transition-metal direct deoxygenation of 1,2-dicarbonyl compounds is chal- catalysts (Rh, Pd, Cu, Au, etc.), are deemed key intermediates lenging. In practice, carbonyl compounds rarely serve as [*] L.-Y. Cao, J.-N. Luo, J.-S. Yao, D.-K. Wang, Y.-Q. Dong, Prof. Dr. C.-X. Zhuo State Key Laboratory of Physical Chemistry of Solid Surfaces Key Laboratory of Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 (P. R. China) E-mail: [email protected] Prof. Dr. C. Zheng State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Shanghai 200032 (P. R. China) Supporting information and the ORCID identification number for one of the authors of this article can be found under: Figure 1. Representative natural products and pharmaceuticals con- https://doi.org/10.1002/anie.202103429. taining a cyclopropane ring. Angew. Chem. Int. Ed. 2021, 60, 1 – 7 2021 Wiley-VCH GmbH 1 These are not the final page numbers! Ü Ü Angewandte Communications Chemie Scheme 2. Proof of concept. these reaction conditions, the deoxygenative cyclopropana- tion of 1a occurred with moderate conversion, thereby providing the desired cyclopropane 2aas a single regioisomer (2a/2a’ > 99:1) in 30% yield (judged by NMR spectroscopy) and the 1,3-oxazine derivative 3a, which was formed by a keto-ene/cyclization tandem reaction[14] in 18% yield (by NMR spectroscopy). The structures of 2a and 3a were unambiguously confirmed by X-ray crystallographic analy- ses.[15] Notably, the probably competitive CÀH insertion product 2a’’ was not detected at all under these conditions. Encouraged by these results, we carried out further optimization of the reaction conditions (Table 1). Various commercially available molybdenum catalysts were investi- gated (entries 2–7). Interestingly, a Mo catalyst system derived from Mo(CO)6 and 3,5-di-tert-butyl-o-benzoquinone, which was elegantly developed by Asako, Takai et al. for the syntheses of indolines, indoles, and pyridoisoindoles,[12j,k] was Scheme 1. 1,2-Dicarbonyl or monocarbonyl compounds directly serve found to catalyze the deoxygenative cyclopropanation of 1a as surrogates for diazo compounds in Mo-catalyzed deoxygenative efficiently in the presence of 60 mol% DPPB (entry 7). The cyclopropanation reactions. o-quinone was proposed to oxidize the Mo(CO)6 to the catalytically active molybdenum(II) species.[12f,j] Next, reduc- direct precursors of carbenes, except for a few examples when tants such as phosphine, HBpin, silane, and Me6Si2 were [11] either stoichiometric metal reagents and reductants or low- examined (entries 8–15). Pleasingly, Ph2MeSiH was found to valent transition-metal complexes are used.[12] In addition, to also promote the reaction in good yield (entry 14). Notably, the best of our knowledge, there is no general method for the the cyclopropanation reaction also occurred when the reac- transition-metal-catalyzed regioselective deoxygenation of tion temperature was decreased or the catalyst loading was 1,2-dicarbonyl compounds to generate carbene equivalents reduced (entries 16 and 17). In addition, other transition- which can engage in subsequent cyclopropanation reactions metal carbonyl complexes screened—W(CO)6, Cr(CO)6,Fe2- with unactivated alkenes to produce cyclopropanes. Herein, (CO)9,Ru3(CO)12, and Mn2(CO)10—were found to be inca- we describe the first Mo-catalyzed deoxygenative cyclopro- pable of promoting the transformation, which demonstrated panation of 1,2-dicarbonyl or monocarbonyl compounds the unique efficiency of the Mo catalyst system towards this [16] (Scheme 1C). By using a commercially available molybde- reaction. Finally, conditions (10 mol% Mo(CO)6, 10 mol% num catalyst in the presence of diphosphine or silane as a mild o-quinone, and 0.6 equiv DPPB in toluene at 1208C) were reductant as well as an oxygen acceptor, various substituted identified that were optimal in terms of yield, chemoselectiv- cyclopropanes have been obtained in up to 90% yield and ity, and efficiency. Under these conditions, the cyclopropane with exclusive regioselectivity. 2a was obtained in 83% yield (entry 7). The general feasibility of our Mo-catalyzed regiospecific With the optimized reaction conditions in hand, various deoxygenative cyclopropanation was evaluated using 1,2- substituted 1,2-dicarbonyl compounds 1 were tested to dicarbonyl compound 1a as a model substrate, 10 mol% establish the generality of the process (Table 2). Reactions [13] commercially available MoO2Cl2 as a catalyst and 60 mol% of 1,2-dicarbonyl substrates containing either electron-donat- 1,4-bis(diphenylphosphino)butane (DPPB) as both a reduc- ing or electron-withdrawing groups on the aromatic ring (R1) tant and an oxygen acceptor (Scheme 2). Intriguingly, under attached to the 2-carbonyl moiety all gave the corresponding 2 www.angewandte.org 2021 Wiley-VCH GmbH Angew. Chem. Int. Ed. 2021, 60,1–7 Ü Ü These are not the final page numbers! Angewandte Communications Chemie Table 1: Optimization of the reaction conditions.[a] Table 2: The substrate scope.[a] Entry Mo cat. x Reductant y t Yield[b] [%] [mol%] [equiv] [h] 2a 3a 1 MoO2Cl2 10 DPPB 0.6 12 30 18 2 MoO2(acac)2 10 DPPB 0.6 12 27 trace [c] 3 [Mo(OAc)2]2 5 DPPB 0.6 12 n.d. 15 [c] 4 MoCl5 10 DPPB 0.6 12 n.d. 23 [c] 5 MoO3 10 DPPB 0.6 12 n.d. 21 [c] 6 Mo(CO)6 10 DPPB 0.6 12 n.d. 22 [d] [e] 7 Mo(CO)6 10 DPPB 0.6 12 90 (83) 10 [d] 8 Mo(CO)6 10 DPPE 0.6 12 75 11 [d] 9 Mo(CO)6 10 DCPB 0.6 12 24 18 [d] 10 Mo(CO)6 10 PPh3 1.2 12 66 16 [d] 11 Mo(CO)6 10 PCy3 1.2 12 37 18 [d] 12 Mo(CO)6 10 HBpin 1.2 12 48 8 [d] 13 Mo(CO)6 10 PhMe2SiH 1.2 16 81 7 [d] [e] 14 Mo(CO)6 10 Ph2MeSiH 1.2 16 83 (76) 7 [d] 15 Mo(CO)6 10 Me6Si2 1.2 12 21 17 [d,f] 16 Mo(CO)6 10 DPPB 0.6 12 37 <5 [g] 17 Mo(CO)6 5 DPPB 0.6 30 84 16 [a] Reaction conditions: Mo cat.
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