DOI: 10.1002/asia.201403030
Communication
Cycloaddition Reactions
Efficient Synthesis of Aza-triquinacene Derivatives via Cycloaddition of 2,6-Diazasemibullvalenes with Nitroso Compounds Ming Zhan,[a] Shaoguang Zhang,[a] Zhe Huang,[a] and Zhenfeng Xi*[a, b] those of triquinacene. However, such aza-triquinacene derivatives are basically unknown, with the exception of 10-azatriquinacene as the first heteroanalogue of the isoelectronic parent triquinacene reported by Mascal and co-workers in 2000 (Figure 1).[4a] Notably, the limited experimental and theoretical data demonstrated that 10-azatriquinacene differs from triquinacene in many aspects.[4] 2,6-Diazasemibullvalenes 1 (Table 1) are structurally unique. They are composed of highly strained rings and undergo an extremely rapid degenerate aza-Cope rearrangement.[5–7] Since we recently established efficient methods for the synthesis of 2,6-diazasemibullvalenes, we started to investigate their reaction chemistry with various substrates, such as isocyanides, azides, and diazo compounds.[8] Structurally interesting compounds have been thus synthesized. Our previous results have
Abstract: The reaction between 2,6-diazasemibullvalenes and nitroso compounds was investigated. Aza-triquinacene derivatives of interesting structural and synthetic chemistry were generated highly selectively in good to excellent isolated yields. This reaction, which was rarely found between common aziridine derivatives and nitroso compounds, could be attributed to the rigid polycyclic ring system and the substitution patterns of 2,6-diazasemibullvalenes. D1-Bipyrroline derivatives were formed in excellent yields when these aza-triquinacene derivatives were treated with SmI2.
Triquinacene and its derivatives (Figure 1), which are concave tricyclic hydrocarbon compounds and first prepared by Woodward in 1964, are important in both structural organic chemistry and synthetic chemistry.[1] The possible existence of homoaromatic stabilization in triquinacene had attracted much attention among organic and physical organic chemists in the past half century.[2, 3] If one or more carbon atoms in triquinacene could be replaced by heteroatoms such as the N atom, its aza-analogues (i.e, aza-triquinacene derivatives) might exhibit physical and chemical properties very different from
Table 1. Reaction between 2,6-diazasemibullvalenes and nitroso compounds.
Substrate 1
Yield [%][a]
Product 2
2 a: Ar = Ph 93 2 b: Ar = o-tolyl 83
2 c: Ar = Ph 72 2 d: Ar = o-tolyl 68 Figure 1. Triquinacene and its aza-derivatives. [a] M. Zhan, Dr. S. Zhang, Z. Huang, Prof. Dr. Z. Xi Beijing National Laboratory for Molecular Sciences Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry, Peking University Beijing 100871 (China) Fax: (+ 86) 10-6275-1708 E-mail: [email protected]
2 e: Ar = Ph 72[b] 2 f: Ar = o-tolyl 60[b]
2 g: Ar = Ph 77[b] 2 h: Ar = o-tolyl 64[b]
[b] Prof. Dr. Z. Xi State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry Shanghai 200032 (China) Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/asia.201403030. Chem. Asian J. 2015, 10, 862 – 864
[a] Isolated yield. [b] At a reaction temperature of 90 8C.
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Communication demonstrated that, although most reactions take place at the aziridine moiety of 2,6-diazasemibullvalenes, they are very much different, or totally different in some cases, from those of standard aziridines, probably due to the rigid polycyclic ring systems of 2,6-diazasemibullvalenes. As our continued interest in the exploration of the reaction chemistry and synthetic applications of 2,6-diazasemibullvalenes, we carried out the reaction between 2,6-diazasemibullvalenes and nitroso compounds, expecting the formation of structurally interesting polycyclic aza-compounds. However, although the reaction chemistry of aziridine and derivatives has been well investigated,[9–12] there is only one report on its reaction with nitroso compounds.[13] In this work, we found that the reaction between 2,6-diazasemibullvalenes and nitroso compounds proceeded smoothly and cleanly, affording 2,5,8-triaza-3-oxa-triquinacene derivatives 2 highly selectively in good to excellent isolated yields via a reaction pathway different to that of previously reported reactions.[7, 8] The reaction between 2,6-diazasemibullvalene 1 a and nitrosobenzene, as monitored by 1H NMR spectroscopy, took place in C6D6 at 60 8C and was completed within 2 h, affording the product 2 a in almost quantitative NMR yield (Table 1). Both benzene and toluene as the solvent afforded the same product. The reaction was very clean, providing product 2 a in 93 % isolated yield. Single-crystal X-ray structural analysis of 2 a demonstrated a three five-membered-ring fused bowl-like structure (Figure 2). Similarly, the 2,6-diazasemibullvalene derivative 1 b could react with PhNO or o-tolylNO smoothly, affording the corresponding products 2 c and 2 d in 72 % and 68 % isolated yields, respectively. However, for the reaction of 1 c and 1 d, a higher reaction temperature (90 8C) was required to ensure a complete reaction.
Scheme 1. A proposed reaction mechanism.
The oxygen atom is electron-rich and cannot accept the lone pair from the anionic nitrogen in intermediate 3. Then fragmentation of one C¢C bond in 3 would lead to the formation of nitrone 4 as a key intermediate,[8a] which would be followed +2] exo cycloaddition reacimmediately by an intramolecular [3+ tion to generate the final product 2. The substitutions including the six-membered ring of nitrone 4 controlled the diaste+2] cycloaddition reaction. reoselectivity of this [3+ D1-Pyrroline derivatives can serve as building blocks for many biologically relevant compounds and as important synthetic intermediates in organic synthesis.[14] But there are few reports about the synthesis of D1-bipyrrolines,[15] especially for functional group-substituted D1-bipyrrolines. We envisioned that the N¢O bond in 2 could be easily cleaved to form substituted D1-bipyrroline derivatives. Indeed, when the isolated products 2 a and 2 b were treated with SmI2 in THF at room temperature, the N¢O bond cleavage took place, affording the functional group-substituted D1-bipyrrolines 5 in excellent isolated yields (Scheme 2). The structure of 5 a was determined by single-crystal X-ray structural analysis (Figure 3). In summary, we have developed an efficient synthetic method for a type of aza-triquinacene derivatives from the reaction between 2,6-diazasemibullvalenes and nitroso compounds. This finding indicates that other types of aza-triquinacene derivatives might be prepared following a similar strategy.
Figure 2. ORTEP drawing of 2 a with 30 % thermal ellipsoids. Hydrogen atoms are omitted for clarity. Selected bond lengths [æ]: O(1)–N(1) 1.454(3), O(1)–C(8) 1.475(4), N(1)–C(13) 1.461(4), C(7)–C(13) 1.525(4), N(2)–C(6) 1.280(4), N(2)–C(8) 1.473(4), C(13)–C(14) 1.527(4), N(3)–C(1) 1.491(4), N(3)– C(14) 1.272(4), C(1)–C(6) 1.518(4), C(1)–C(7) 1.533(4), C(7)–C(8) 1.539(4).
Scheme 2. Further application of 2.
Experimental Section
The structure of products 2 indicated that a novel rearrangement, instead of the normal [3+ +2] cycloaddition,[13] took place during the reaction. A proposed reaction mechanism is given in Scheme 1. At first, the nitrogen atom of the nitroso group would attack the aziridine moiety of the 2,6-diazasemibullvalene, opening the three-membered aziridine ring to form 3. Chem. Asian J. 2015, 10, 862 – 864
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General procedure for the reaction of 2,6-diazasemibullvalene 1 with a nitroso compound A nitroso compound (0.6 mmol) was added to 2,6-diazasemibullvalene 1 (0.5 mmol) in toluene (2 mL), and the reaction mixture was
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Communication [3] L. A. Paquette, Chem. Rev. 1989, 89, 1051 – 1065. [4] a) M. Mascal, M. Lera, A. J. Blake, J. Org. Chem. 2000, 65, 7253 – 7255; b) H. Jiao, J.-F. Halet, J. A. Gladysz, J. Org. Chem. 2001, 66, 3902 – 3905; c) M. Mascal, J. C. Bertran, J. Am. Chem. Soc. 2005, 127, 1352 – 1353; d) D. Pham, J. C. Bertran, M. M. Olmstead, M. Mascal, A. L. Balch, Org. Lett. 2005, 7, 2805 – 2808; e) M. Mascal, J. Org. Chem. 2007, 72, 4323 – 4327. [5] For theoretical studies on 2,6-diazasemibullvalenes, see: a) M. J. S. Dewar, Z. Nhlovsk, B. D. Nhlovsky´, J. Chem. Soc. Chem. Commun. 1971, 1377 – 1378; b) D. R. Greve, J. Phys. Org. Chem. 2011, 24, 222 – 228. [6] For experimental studies on 2,6-diazasemibullvalenes, see: a) C. Schnieders, H. J. Altenbach, K. Mìllen, Angew. Chem. Int. Ed. Engl. 1982, 21, 637 – 638; Angew. Chem. 1982, 94, 638 – 639; b) C. Schnieders, W. Huber, J. Lex, K. Mìllen, Angew. Chem. Int. Ed. Engl. 1985, 24, 576 – 577; Angew. Chem. 1985, 97, 579 – 580; c) B. Dìll, K. Mìllen, Tetrahedron Lett. 1992, 33, 8047 – 8050. [7] a) S. Zhang, J. Wei, M. Zhan, Q. Luo, C. Wang, W.-X. Zhang, Z. Xi, J. Am. Chem. Soc. 2012, 134, 11964 – 11967. See also: b) C. Wang, J. Yuan, G. Li, Z. Wang, S. Zhang, Z. Xi, J. Am. Chem. Soc. 2006, 128, 4564 – 4565; c) S. Zhang, M. Zhan, Q. Wang, C. Wang, W.-X. Zhang, Z. Xi, Org. Chem. Front. 2014, 1, 130 – 134. [8] a) S. Zhang, W.-X. Zhang, Z. Xi, Angew. Chem. Int. Ed. 2013, 52, 3485 – 3489; Angew. Chem. 2013, 125, 3569 – 3573; b) S. Zhang, M. Zhan, W.-X. Zhang, Z. Xi, Chem. Commun. 2013, 49, 6146 – 6148; c) S. Zhang, M. Zhan, W.-X. Zhang, Z. Xi, Chem. Eur. J. 2014, 20, 9744 – 9752. [9] For reviews on cycloaddition reactions of aziridines, see: a) P. Dauban, G. Malik, Angew. Chem. Int. Ed. 2009, 48, 9026 – 9029; Angew. Chem. 2009, 121, 9188 – 9191; b) I. Coldham, R. Hufton, Chem. Rev. 2005, 105, 2765 – 2810; c) C. Y. Huang, A. G. Doyle, Chem. Rev. 2014, 114, 8153 – 8198. See also: d) J.-Y. Wu, Z.-B. Luo, L.-X. Dai, X.-L. Hou, J. Org. Chem. 2008, 73, 9137 – 9139; e) Y. Du, Y. Wu, A.-H. Liu, L.-N. He, J. Org. Chem. 2008, 73, 4709 – 4712; f) X. Wu, J. Zhang, Synthesis 2012, 2147 – 2154. [10] For a recent review on nucleophilic ring opening of aziridine, see: a) S. Stankovic´, M. D’hooghe, S. Catak, H. Eum, M. Waroquier, V. Van Speybroeck, N. De Kimpe, H.-J. Ha, Chem. Soc. Rev. 2012, 41, 643 – 665. See also: b) R.-H. Fan, X.-L. Hou, J. Org. Chem. 2003, 68, 726 – 730; c) R.-H. Fan, Y.-G. Zhou, W.-X. Zhang, X.-L. Hou, L.-X. Dai, J. Org. Chem. 2004, 69, 335 – 338; d) J.-Y. Wang, D.-X. Wang, Q.-Y. Zheng, Z.-T. Huang, M.-X. Wang, J. Org. Chem. 2007, 72, 2040 – 2045; e) D.-D. Chen, X.-L. Hou, L.-X. Dai, J. Org. Chem. 2008, 73, 5578 – 5581; f) J.-Y. Wang, Y. Hu, D.-X. Wang, J. Pan, Z.-T. Huang, M.-X. Wang, Chem. Commun. 2009, 422 – 424; g) L. Wei, J. Zhang, Chem. Commun. 2012, 48, 2636 – 2638; h) Z. Zhang, D. Wang, Y. Wei, M. Shi, Chem. Commun. 2012, 48, 9607 – 9609; i) H. Lee, J. H. Kim, W. K. Lee, J. Cho, W. Nam, J. Lee, H.-J. Ha, Org. Biomol. Chem. 2013, 11, 3629 – 3634. [11] I. D. G. Watson, L. Yu, A. K. Yudin, Acc. Chem. Res. 2006, 39, 194 – 206. [12] For selected reports on reactions of N-alkenyl aziridines, see: a) M. Sasaki, A. K. Yudin, J. Am. Chem. Soc. 2003, 125, 14242 – 14243; b) S. Dalili, A. K. Yudin, Org. Lett. 2005, 7, 1161 – 1164; c) G. Chen, M. Sasaki, X. Li, A. K. Yudin, J. Org. Chem. 2006, 71, 6067 – 6073; d) M. R. Siebert, A. K. Yudin, D. J. Tantillo, Org. Lett. 2008, 10, 57 – 60; e) K. Okamoto, T. Oda, S. Kohigashi, K. Ohe, Angew. Chem. Int. Ed. 2011, 50, 11470 – 11473; Angew. Chem. 2011, 123, 11672 – 11675; f) M.-K. Ji, D. Hertsen, D.-H. Yoon, H. Eum, H. Goossens, M. Waroquier, V. V. Speybroeck, M. D’hooghe, N. De Kimpe, H.-J. Ha, Chem. Asian J. 2014, 9, 1060 – 1067. [13] J. W. Lown, J. P. Moser, J. Chem. Soc. Chem. Commun. 1970, 247 – 248. [14] a) W. Miltyk, J. A. Palka, Comp. Biochem. Physiol. Part A 2000, 125, 265 – 271; b) A. Stapon, R. Li, C. A. Townsend, J. Am. Chem. Soc. 2003, 125, 8486 – 8493. [15] a) R. B. Bates, B. Gordon, III, P. C. Keller, J. V. Rund, N. S. Mills, J. Org. Chem. 1980, 45, 168 – 169; b) N. Yu, C. Wang, F. Zhao, L. Liu, W.-X. Zhang, Z. Xi, Chem. Eur. J. 2008, 14, 5670 – 5679; c) G. A. Abakumov, V. K. Cherkasov, N. O. Druzhkov, T. N. Kocherova, A. S. Shavyrin, Russ. Chem. Bull. 2011, 60, 112 – 117; d) J. J. Eisch, K. Yu, A. L. Rheingold, Eur. J. Org. Chem. 2012, 3165 – 3171.
Figure 3. ORTEP drawing of 5 a with 30 % thermal ellipsoids. Hydrogen atoms are omitted for clarity. Selected bond lengths [æ]: O(1)–C(3) 1.417(2), N(1)–C(1) 1.482(2), N(1)–C(6) 1.274(2), N(2)–C(2) 1.274(2), N(2)–C(3) 1.484(2), N(3)–C(5) 1.447(2), C(1)–C(2) 1.508(3), C(1)–C(4) 1.540(2), C(3)–C(4) 1.567(2), C(4)–C(5) 1.543(2), C(5)–C(6) 1.532(2).
stirred at 60 8C or 90 8C for 2 h. After removal of the solvent in vacuum, purification by column chromatography on silica gel (petroleum ether/EtOAc/triethylamine = 100:3:1) gave 2 as pure products.
General procedure for reduction of 2 with SmI2 2,5,8-Triaza-3-oxa-triquinacene 2 (0.5 mmol) was dissolved in THF (2 mL). A solution of SmI2 in THF (1.5 mmol, 0.1 m in THF) was added to the solution of 2 dropwise, and the reaction mixture was stirred at room temperature for 12 h. After quenching by water, the reaction mixture was extracted with EtOAc (10 mL Õ 3) and washed with water (15 mL) and saturated aqueous NaCl (15 mL). The combined organic layers were then dried over MgSO4. The mixture was then concentrated in vacuo, and the residue was purified by chromatography on silica gel (petroleum ether/EtOAc/triethylamine = 100:20:1) to afford 5 as pure products.
Acknowledgements This work was partially supported by the 973 Program (2012CB821600) and the National Natural Science Foundation of China (NSFC). Keywords: aza-triquinacene · cycloaddition diazasemibullvalene · nitroso compound · d1-bipyrroline
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[1] a) R. B. Woodward, T. Fukunaga, R. C. Kelly, J. Am. Chem. Soc. 1964, 86, 3162 – 3164; b) I. T. Jacobson, Acta Chem. Scand. 1967, 21, 2235 – 2246; c) H. Hopf, Classics in Hydrocarbon Chemistry, Wiley-VCH, Weinheim, 2000; d) R. Haag, A. de Meijere, Top. Curr. Chem. 1998, 196, 137 – 165; e) D. Kuck, Chem. Rev. 2006, 106, 4885 – 4925. [2] a) J. F. Liebman, L. A. Paquette, J. R. Peterson, D. W. Rogers, J. Am. Chem. Soc. 1986, 108, 8267 – 8268; b) M. A. Miller, J. M. Schulman, R. L. Disch, J. Am. Chem. Soc. 1988, 110, 7681 – 7684; c) M. J. S. Dewar, A. J. Holder, J. Am. Chem. Soc. 1989, 111, 5384 – 5387; d) J. W. Storer, K. N. Houk, J. Am. Chem. Soc. 1992, 114, 1165 – 1168; e) S. P. Verevkin, H.-D. Beckhaus, C. Rìchardt, R. Haag, S. I. Kozhushkov, T. Zywietz, A. de Meijere, H. Jiao, P. v. R. Schleyer, J. Am. Chem. Soc. 1998, 120, 11130 – 11135. Chem. Asian J. 2015, 10, 862 – 864
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Received: September 3, 2014 Revised: October 20, 2014 Published online on November 12, 2014
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Communication
Cycloaddition Reactions
Efficient Synthesis of Aza-triquinacene Derivatives via Cycloaddition of 2,6-Diazasemibullvalenes with Nitroso Compounds Ming Zhan,[a] Shaoguang Zhang,[a] Zhe Huang,[a] and Zhenfeng Xi*[a, b] those of triquinacene. However, such aza-triquinacene derivatives are basically unknown, with the exception of 10-azatriquinacene as the first heteroanalogue of the isoelectronic parent triquinacene reported by Mascal and co-workers in 2000 (Figure 1).[4a] Notably, the limited experimental and theoretical data demonstrated that 10-azatriquinacene differs from triquinacene in many aspects.[4] 2,6-Diazasemibullvalenes 1 (Table 1) are structurally unique. They are composed of highly strained rings and undergo an extremely rapid degenerate aza-Cope rearrangement.[5–7] Since we recently established efficient methods for the synthesis of 2,6-diazasemibullvalenes, we started to investigate their reaction chemistry with various substrates, such as isocyanides, azides, and diazo compounds.[8] Structurally interesting compounds have been thus synthesized. Our previous results have
Abstract: The reaction between 2,6-diazasemibullvalenes and nitroso compounds was investigated. Aza-triquinacene derivatives of interesting structural and synthetic chemistry were generated highly selectively in good to excellent isolated yields. This reaction, which was rarely found between common aziridine derivatives and nitroso compounds, could be attributed to the rigid polycyclic ring system and the substitution patterns of 2,6-diazasemibullvalenes. D1-Bipyrroline derivatives were formed in excellent yields when these aza-triquinacene derivatives were treated with SmI2.
Triquinacene and its derivatives (Figure 1), which are concave tricyclic hydrocarbon compounds and first prepared by Woodward in 1964, are important in both structural organic chemistry and synthetic chemistry.[1] The possible existence of homoaromatic stabilization in triquinacene had attracted much attention among organic and physical organic chemists in the past half century.[2, 3] If one or more carbon atoms in triquinacene could be replaced by heteroatoms such as the N atom, its aza-analogues (i.e, aza-triquinacene derivatives) might exhibit physical and chemical properties very different from
Table 1. Reaction between 2,6-diazasemibullvalenes and nitroso compounds.
Substrate 1
Yield [%][a]
Product 2
2 a: Ar = Ph 93 2 b: Ar = o-tolyl 83
2 c: Ar = Ph 72 2 d: Ar = o-tolyl 68 Figure 1. Triquinacene and its aza-derivatives. [a] M. Zhan, Dr. S. Zhang, Z. Huang, Prof. Dr. Z. Xi Beijing National Laboratory for Molecular Sciences Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education College of Chemistry, Peking University Beijing 100871 (China) Fax: (+ 86) 10-6275-1708 E-mail: [email protected]
2 e: Ar = Ph 72[b] 2 f: Ar = o-tolyl 60[b]
2 g: Ar = Ph 77[b] 2 h: Ar = o-tolyl 64[b]
[b] Prof. Dr. Z. Xi State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry Shanghai 200032 (China) Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/asia.201403030. Chem. Asian J. 2015, 10, 862 – 864
[a] Isolated yield. [b] At a reaction temperature of 90 8C.
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Communication demonstrated that, although most reactions take place at the aziridine moiety of 2,6-diazasemibullvalenes, they are very much different, or totally different in some cases, from those of standard aziridines, probably due to the rigid polycyclic ring systems of 2,6-diazasemibullvalenes. As our continued interest in the exploration of the reaction chemistry and synthetic applications of 2,6-diazasemibullvalenes, we carried out the reaction between 2,6-diazasemibullvalenes and nitroso compounds, expecting the formation of structurally interesting polycyclic aza-compounds. However, although the reaction chemistry of aziridine and derivatives has been well investigated,[9–12] there is only one report on its reaction with nitroso compounds.[13] In this work, we found that the reaction between 2,6-diazasemibullvalenes and nitroso compounds proceeded smoothly and cleanly, affording 2,5,8-triaza-3-oxa-triquinacene derivatives 2 highly selectively in good to excellent isolated yields via a reaction pathway different to that of previously reported reactions.[7, 8] The reaction between 2,6-diazasemibullvalene 1 a and nitrosobenzene, as monitored by 1H NMR spectroscopy, took place in C6D6 at 60 8C and was completed within 2 h, affording the product 2 a in almost quantitative NMR yield (Table 1). Both benzene and toluene as the solvent afforded the same product. The reaction was very clean, providing product 2 a in 93 % isolated yield. Single-crystal X-ray structural analysis of 2 a demonstrated a three five-membered-ring fused bowl-like structure (Figure 2). Similarly, the 2,6-diazasemibullvalene derivative 1 b could react with PhNO or o-tolylNO smoothly, affording the corresponding products 2 c and 2 d in 72 % and 68 % isolated yields, respectively. However, for the reaction of 1 c and 1 d, a higher reaction temperature (90 8C) was required to ensure a complete reaction.
Scheme 1. A proposed reaction mechanism.
The oxygen atom is electron-rich and cannot accept the lone pair from the anionic nitrogen in intermediate 3. Then fragmentation of one C¢C bond in 3 would lead to the formation of nitrone 4 as a key intermediate,[8a] which would be followed +2] exo cycloaddition reacimmediately by an intramolecular [3+ tion to generate the final product 2. The substitutions including the six-membered ring of nitrone 4 controlled the diaste+2] cycloaddition reaction. reoselectivity of this [3+ D1-Pyrroline derivatives can serve as building blocks for many biologically relevant compounds and as important synthetic intermediates in organic synthesis.[14] But there are few reports about the synthesis of D1-bipyrrolines,[15] especially for functional group-substituted D1-bipyrrolines. We envisioned that the N¢O bond in 2 could be easily cleaved to form substituted D1-bipyrroline derivatives. Indeed, when the isolated products 2 a and 2 b were treated with SmI2 in THF at room temperature, the N¢O bond cleavage took place, affording the functional group-substituted D1-bipyrrolines 5 in excellent isolated yields (Scheme 2). The structure of 5 a was determined by single-crystal X-ray structural analysis (Figure 3). In summary, we have developed an efficient synthetic method for a type of aza-triquinacene derivatives from the reaction between 2,6-diazasemibullvalenes and nitroso compounds. This finding indicates that other types of aza-triquinacene derivatives might be prepared following a similar strategy.
Figure 2. ORTEP drawing of 2 a with 30 % thermal ellipsoids. Hydrogen atoms are omitted for clarity. Selected bond lengths [æ]: O(1)–N(1) 1.454(3), O(1)–C(8) 1.475(4), N(1)–C(13) 1.461(4), C(7)–C(13) 1.525(4), N(2)–C(6) 1.280(4), N(2)–C(8) 1.473(4), C(13)–C(14) 1.527(4), N(3)–C(1) 1.491(4), N(3)– C(14) 1.272(4), C(1)–C(6) 1.518(4), C(1)–C(7) 1.533(4), C(7)–C(8) 1.539(4).
Scheme 2. Further application of 2.
Experimental Section
The structure of products 2 indicated that a novel rearrangement, instead of the normal [3+ +2] cycloaddition,[13] took place during the reaction. A proposed reaction mechanism is given in Scheme 1. At first, the nitrogen atom of the nitroso group would attack the aziridine moiety of the 2,6-diazasemibullvalene, opening the three-membered aziridine ring to form 3. Chem. Asian J. 2015, 10, 862 – 864
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General procedure for the reaction of 2,6-diazasemibullvalene 1 with a nitroso compound A nitroso compound (0.6 mmol) was added to 2,6-diazasemibullvalene 1 (0.5 mmol) in toluene (2 mL), and the reaction mixture was
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Communication [3] L. A. Paquette, Chem. Rev. 1989, 89, 1051 – 1065. [4] a) M. Mascal, M. Lera, A. J. Blake, J. Org. Chem. 2000, 65, 7253 – 7255; b) H. Jiao, J.-F. Halet, J. A. Gladysz, J. Org. Chem. 2001, 66, 3902 – 3905; c) M. Mascal, J. C. Bertran, J. Am. Chem. Soc. 2005, 127, 1352 – 1353; d) D. Pham, J. C. Bertran, M. M. Olmstead, M. Mascal, A. L. Balch, Org. Lett. 2005, 7, 2805 – 2808; e) M. Mascal, J. Org. Chem. 2007, 72, 4323 – 4327. [5] For theoretical studies on 2,6-diazasemibullvalenes, see: a) M. J. S. Dewar, Z. Nhlovsk, B. D. Nhlovsky´, J. Chem. Soc. Chem. Commun. 1971, 1377 – 1378; b) D. R. Greve, J. Phys. Org. Chem. 2011, 24, 222 – 228. [6] For experimental studies on 2,6-diazasemibullvalenes, see: a) C. Schnieders, H. J. Altenbach, K. Mìllen, Angew. Chem. Int. Ed. Engl. 1982, 21, 637 – 638; Angew. Chem. 1982, 94, 638 – 639; b) C. Schnieders, W. Huber, J. Lex, K. Mìllen, Angew. Chem. Int. Ed. Engl. 1985, 24, 576 – 577; Angew. Chem. 1985, 97, 579 – 580; c) B. Dìll, K. Mìllen, Tetrahedron Lett. 1992, 33, 8047 – 8050. [7] a) S. Zhang, J. Wei, M. Zhan, Q. Luo, C. Wang, W.-X. Zhang, Z. Xi, J. Am. Chem. Soc. 2012, 134, 11964 – 11967. See also: b) C. Wang, J. Yuan, G. Li, Z. Wang, S. Zhang, Z. Xi, J. Am. Chem. Soc. 2006, 128, 4564 – 4565; c) S. Zhang, M. Zhan, Q. Wang, C. Wang, W.-X. Zhang, Z. Xi, Org. Chem. Front. 2014, 1, 130 – 134. [8] a) S. Zhang, W.-X. Zhang, Z. Xi, Angew. Chem. Int. Ed. 2013, 52, 3485 – 3489; Angew. Chem. 2013, 125, 3569 – 3573; b) S. Zhang, M. Zhan, W.-X. Zhang, Z. Xi, Chem. Commun. 2013, 49, 6146 – 6148; c) S. Zhang, M. Zhan, W.-X. Zhang, Z. Xi, Chem. Eur. J. 2014, 20, 9744 – 9752. [9] For reviews on cycloaddition reactions of aziridines, see: a) P. Dauban, G. Malik, Angew. Chem. Int. Ed. 2009, 48, 9026 – 9029; Angew. Chem. 2009, 121, 9188 – 9191; b) I. Coldham, R. Hufton, Chem. Rev. 2005, 105, 2765 – 2810; c) C. Y. Huang, A. G. Doyle, Chem. Rev. 2014, 114, 8153 – 8198. See also: d) J.-Y. Wu, Z.-B. Luo, L.-X. Dai, X.-L. Hou, J. Org. Chem. 2008, 73, 9137 – 9139; e) Y. Du, Y. Wu, A.-H. Liu, L.-N. He, J. Org. Chem. 2008, 73, 4709 – 4712; f) X. Wu, J. Zhang, Synthesis 2012, 2147 – 2154. [10] For a recent review on nucleophilic ring opening of aziridine, see: a) S. Stankovic´, M. D’hooghe, S. Catak, H. Eum, M. Waroquier, V. Van Speybroeck, N. De Kimpe, H.-J. Ha, Chem. Soc. Rev. 2012, 41, 643 – 665. See also: b) R.-H. Fan, X.-L. Hou, J. Org. Chem. 2003, 68, 726 – 730; c) R.-H. Fan, Y.-G. Zhou, W.-X. Zhang, X.-L. Hou, L.-X. Dai, J. Org. Chem. 2004, 69, 335 – 338; d) J.-Y. Wang, D.-X. Wang, Q.-Y. Zheng, Z.-T. Huang, M.-X. Wang, J. Org. Chem. 2007, 72, 2040 – 2045; e) D.-D. Chen, X.-L. Hou, L.-X. Dai, J. Org. Chem. 2008, 73, 5578 – 5581; f) J.-Y. Wang, Y. Hu, D.-X. Wang, J. Pan, Z.-T. Huang, M.-X. Wang, Chem. Commun. 2009, 422 – 424; g) L. Wei, J. Zhang, Chem. Commun. 2012, 48, 2636 – 2638; h) Z. Zhang, D. Wang, Y. Wei, M. Shi, Chem. Commun. 2012, 48, 9607 – 9609; i) H. Lee, J. H. Kim, W. K. Lee, J. Cho, W. Nam, J. Lee, H.-J. Ha, Org. Biomol. Chem. 2013, 11, 3629 – 3634. [11] I. D. G. Watson, L. Yu, A. K. Yudin, Acc. Chem. Res. 2006, 39, 194 – 206. [12] For selected reports on reactions of N-alkenyl aziridines, see: a) M. Sasaki, A. K. Yudin, J. Am. Chem. Soc. 2003, 125, 14242 – 14243; b) S. Dalili, A. K. Yudin, Org. Lett. 2005, 7, 1161 – 1164; c) G. Chen, M. Sasaki, X. Li, A. K. Yudin, J. Org. Chem. 2006, 71, 6067 – 6073; d) M. R. Siebert, A. K. Yudin, D. J. Tantillo, Org. Lett. 2008, 10, 57 – 60; e) K. Okamoto, T. Oda, S. Kohigashi, K. Ohe, Angew. Chem. Int. Ed. 2011, 50, 11470 – 11473; Angew. Chem. 2011, 123, 11672 – 11675; f) M.-K. Ji, D. Hertsen, D.-H. Yoon, H. Eum, H. Goossens, M. Waroquier, V. V. Speybroeck, M. D’hooghe, N. De Kimpe, H.-J. Ha, Chem. Asian J. 2014, 9, 1060 – 1067. [13] J. W. Lown, J. P. Moser, J. Chem. Soc. Chem. Commun. 1970, 247 – 248. [14] a) W. Miltyk, J. A. Palka, Comp. Biochem. Physiol. Part A 2000, 125, 265 – 271; b) A. Stapon, R. Li, C. A. Townsend, J. Am. Chem. Soc. 2003, 125, 8486 – 8493. [15] a) R. B. Bates, B. Gordon, III, P. C. Keller, J. V. Rund, N. S. Mills, J. Org. Chem. 1980, 45, 168 – 169; b) N. Yu, C. Wang, F. Zhao, L. Liu, W.-X. Zhang, Z. Xi, Chem. Eur. J. 2008, 14, 5670 – 5679; c) G. A. Abakumov, V. K. Cherkasov, N. O. Druzhkov, T. N. Kocherova, A. S. Shavyrin, Russ. Chem. Bull. 2011, 60, 112 – 117; d) J. J. Eisch, K. Yu, A. L. Rheingold, Eur. J. Org. Chem. 2012, 3165 – 3171.
Figure 3. ORTEP drawing of 5 a with 30 % thermal ellipsoids. Hydrogen atoms are omitted for clarity. Selected bond lengths [æ]: O(1)–C(3) 1.417(2), N(1)–C(1) 1.482(2), N(1)–C(6) 1.274(2), N(2)–C(2) 1.274(2), N(2)–C(3) 1.484(2), N(3)–C(5) 1.447(2), C(1)–C(2) 1.508(3), C(1)–C(4) 1.540(2), C(3)–C(4) 1.567(2), C(4)–C(5) 1.543(2), C(5)–C(6) 1.532(2).
stirred at 60 8C or 90 8C for 2 h. After removal of the solvent in vacuum, purification by column chromatography on silica gel (petroleum ether/EtOAc/triethylamine = 100:3:1) gave 2 as pure products.
General procedure for reduction of 2 with SmI2 2,5,8-Triaza-3-oxa-triquinacene 2 (0.5 mmol) was dissolved in THF (2 mL). A solution of SmI2 in THF (1.5 mmol, 0.1 m in THF) was added to the solution of 2 dropwise, and the reaction mixture was stirred at room temperature for 12 h. After quenching by water, the reaction mixture was extracted with EtOAc (10 mL Õ 3) and washed with water (15 mL) and saturated aqueous NaCl (15 mL). The combined organic layers were then dried over MgSO4. The mixture was then concentrated in vacuo, and the residue was purified by chromatography on silica gel (petroleum ether/EtOAc/triethylamine = 100:20:1) to afford 5 as pure products.
Acknowledgements This work was partially supported by the 973 Program (2012CB821600) and the National Natural Science Foundation of China (NSFC). Keywords: aza-triquinacene · cycloaddition diazasemibullvalene · nitroso compound · d1-bipyrroline
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[1] a) R. B. Woodward, T. Fukunaga, R. C. Kelly, J. Am. Chem. Soc. 1964, 86, 3162 – 3164; b) I. T. Jacobson, Acta Chem. Scand. 1967, 21, 2235 – 2246; c) H. Hopf, Classics in Hydrocarbon Chemistry, Wiley-VCH, Weinheim, 2000; d) R. Haag, A. de Meijere, Top. Curr. Chem. 1998, 196, 137 – 165; e) D. Kuck, Chem. Rev. 2006, 106, 4885 – 4925. [2] a) J. F. Liebman, L. A. Paquette, J. R. Peterson, D. W. Rogers, J. Am. Chem. Soc. 1986, 108, 8267 – 8268; b) M. A. Miller, J. M. Schulman, R. L. Disch, J. Am. Chem. Soc. 1988, 110, 7681 – 7684; c) M. J. S. Dewar, A. J. Holder, J. Am. Chem. Soc. 1989, 111, 5384 – 5387; d) J. W. Storer, K. N. Houk, J. Am. Chem. Soc. 1992, 114, 1165 – 1168; e) S. P. Verevkin, H.-D. Beckhaus, C. Rìchardt, R. Haag, S. I. Kozhushkov, T. Zywietz, A. de Meijere, H. Jiao, P. v. R. Schleyer, J. Am. Chem. Soc. 1998, 120, 11130 – 11135. Chem. Asian J. 2015, 10, 862 – 864
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Received: September 3, 2014 Revised: October 20, 2014 Published online on November 12, 2014
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