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CC BY-NC-ND 4.0 · Synlett 2017; 28(20): 2946-2950
DOI: 10.1055/s-0036-1588524
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Intermolecular [2+2] Photocycloaddition of β-Nitrostyrenes to Olefins upon Irradiation with Visible Light

Lisa-Marie Mohr
,
Thorsten Bach  *
Financial support by the European Research Council under the European Union’s Horizon 2020 research and innovation programme (grant agreement No 665951 – ELICOS) is gratefully acknowledged.
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Publication History

Received: 19 June 2017

Accepted after revision: 30 June 2017

Publication Date:
31 August 2017 (online)

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Dedicated to Victor Snieckus, a dear colleague and friend, on the occasion of his 80th birthday

Abstract

The title compounds were found to undergo a [2+2] photocycloaddition with olefins at λ = 419 nm in CH2Cl2 as the solvent. The resulting cyclobutanes were isolated in yields of 32–87% (11 examples) and showed a defined relative configuration at C1/C4 in the major dia­stereoisomer (nitro and aryl trans). The analysis of side products and triplet sensitization experiments support a mechanistic scenario in which a 1,4-diradical is formed as a key intermediate.

Key words

cycloaddition - cyclobutanes - diastereoselectivity - nitro compounds - photochemistry - stereoselective synthesis - umpolung - visible light

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1588524.
  • Supporting Information

Primary Data

    Primary data for this article are available online at https://zenodo.org/record/4610511 and can be cited using the following DOI: 10.5281/zenodo.4610511. Please note that the DOI for the Primary Data associated with this article was updated on April 20, 2021.

  • Primary Data
 

  • References and Notes

  • 1 Poplata S. Tröster A. Zou Y.-Q. Bach T. Chem. Rev. 2016; 116: 9748
  • 2 Roth HD. Angew. Chem., Int. Ed. Engl. 1989; 28: 1193
    • 3a Lennartson A. Roffey A. Moth-Poulsen K. Tetrahedron Lett. 2015; 56: 1457
    • 3b Dubonosov AD. Bren VA. Chernoivanov VA. Russ. Chem. Rev. 2002; 71: 917
    • 4a Barwise AJ. G. Gorman AA. Leyland RL. Smith PG. Rodgers MA. J. J. Am. Chem. Soc. 1978; 100: 1814
    • 4b Jones II. G. Chiang S.-H. Xuan PT. J. Photochem. 1979; 10: 1
    • 5a Ikezawa H. Kutal C. Yasufuku K. Yamazaki H. J. Am. Chem. Soc. 1986; 108: 1589
    • 5b Grutsch PA. Kutal C. J. Am. Chem. Soc. 1986; 108: 3108
    • 5c Sluggett GW. Turro NJ. Roth HD. J. Phys. Chem. A 1997; 101: 8834
    • 6a Brimioulle R. Lenhart D. Maturi MM. Bach T. Angew. Chem. Int. Ed. 2015; 54: 3872
    • 6b Meggers E. Chem. Commun. 2015; 51: 3290
    • 7a Zou Y.-Q. Duan S.-W. Meng X.-G. Hu X.-Q. Gao S. Chen J.-R. Xiao W.-J. Tetrahedron 2012; 68: 6914
    • 7b Lu Z. Yoon TP. Angew. Chem. Int. Ed. 2012; 51: 10329
    • 7c Kumarasamy E. Raghunathan R. Jockusch S. Ugrinov A. Sivaguru J. J. Am. Chem. Soc. 2014; 136: 8729
    • 7d Hurtley AE. Lu Z. Yoon TP. Angew. Chem. Int. Ed. 2014; 53: 8991
    • 7e Liu Q. Zhu F.-P. Jin X.-L. Wang X.-J. Chen H. Wu L.-Z. Chem. Eur. J. 2015; 21: 10326
    • 7f Mojr V. Svobodová E. Straková K. Neveselý T. Chudoba J. Dvořáková H. Cibulka R. Chem. Commun. 2015; 51: 12036
    • 8a Alonso R. Bach T. Angew. Chem. Int. Ed. 2014; 53: 4368
    • 8b Tröster A. Alonso R. Bauer A. Bach T. J. Am. Chem. Soc. 2016; 138: 7808
    • 8c Blum TR. Miller ZD. Bates DM. Guzei IA. Yoon TP. Science 2016; 354: 1391
    • 9a Guo H. Herdtweck E. Bach T. Angew. Chem. Int. Ed. 2010; 49: 7782
    • 9b Brimioulle R. Bach T. Science 2013; 342: 840
    • 9c Brimioulle R. Bauer A. Bach T. J. Am. Chem. Soc. 2015; 137: 5170
    • 9d Brenninger C. Pöthig A. Bach T. Angew. Chem. Int. Ed. 2017; 56: 4337

      Reviews on the photochemistry of nitro compounds:
    • 10a Ho T.-I. Chow YL. Photochemistry of Nitro and Nitroso Compounds. In The Chemistry of Functional Groups, Supplement F2: The Chemistry of Amino, Nitroso, Nitro and Related Groups. Patai S. Wiley; Chichester: 1996: 747
      Google Scholar
    • 10b Döpp D. Photochemical Reactivity of the Nitro Group. In CRC Handbook of Organic Photochemistry and Photobiology. Horspool WM. Song P.-S. CRC Press; Boca Raton: 1995: 1019
      Google Scholar
    • 11a Priebs B. Justus Liebigs Ann. Chem. 1884; 225: 319
    • 11b Meisenheimer J. Heim F. Justus Liebigs Ann. Chem. 1907; 355: 260
    • 11c Miller DB. Flanagan PW. Shechter H. J. Am. Chem. Soc. 1972; 94: 3912
  • 12 Chapman OL. Griswold AA. Hoganson E. Lenz G. Reasoner J. Pure Appl. Chem. 1964; 9: 585
  • 13 In a later paper, the reaction of trans-β-nitrostyrene (1) and 2,3-dimethylbutadiene (2d) was reported to be performed at λ = 300 nm: Magner JT. Selke M. Russell AA. Chapman OL. J. Chem. Ed. 1996; 73: 854
  • 14 Majima T. Pac C. Sakurai H. J. Am. Chem. Soc. 1980; 102: 5265
  • 15 Ramkumar D. Sankararaman S. J. Chem. Soc., Perkin Trans. 2 1996; 939
  • 16 For a Cr-photocatalytic [4+2] cycloaddition of trans-β-nitro-para-methoxystyrene and 1,3-dienes, see: Stevenson SM. Higgins RF. Shores MP. Ferreira EM. Chem. Sci. 2017; 8: 654
    • 17a Cheng LT. Tam W. Marder SR. Stiegman AE. Rikken G. Spangler CW. J. Phys. Chem. 1991; 95: 10643
    • 17b Aboskalova NI. Smirnova NN. Kataeva ON. Baichurin RI. Fel'gendler AV. Berkova GA. Berestovitskaya VA. Russ. J. Gen. Chem. 2008; 78: 1711
    • 18a Cowley DJ. J. Chem. Soc., Perkin Trans. 2 1975; 1576
    • 18b Zhang S.-Q. Wang H.-G. Pei K.-M. Zheng X. J. Chem. Phys. 2007; 126: 194505

      For further references to the photochemistry of nitroolefins, see:
    • 19a Ried W. Wilk M. Justus Liebigs Ann. Chem. 1954; 590: 111
    • 19b Zimmerman HE. Roberts LC. Arnold R. J. Org. Chem. 1977; 42: 621
    • 19c Humphry-Baker RA. Salisbury K. Wood GP. J. Chem. Soc., Perkin Trans. 2 1978; 659
    • 19d Grant RD. Pinhey JT. Rizzardo E. Smith GC. Aust. J. Chem. 1985; 38: 1505
    • 19e Kassaee MZ. Nassari MA. J. Photochem. Photobiol. A 2000; 136: 41

      For the emission spectra of the lamps, see for λ = 300 nm, 366 nm:
    • 20a Maturi MM. Wenninger M. Alonso R. Bauer A. Pöthig A. Riedle E. Bach T. Chem. Eur. J. 2013; 19: 7461

      • λ = 350 nm:
    • 20b Rimböck K.-H. Pöthig A. Bach T. Synthesis 2015; 47: 2869

      • λ = 419 nm:
    • 20c Alonso R. Bach T. Angew. Chem. Int. Ed. 2014; 53: 4368

      • λ = 457 nm, 470 nm:
    • 20d Lenhart D. Bauer A. Pöthig A. Bach T. Chem. Eur. J. 2016; 22: 6519
  • 21 Representative Procedure 29.8 mg of nitrostyrene 1 (199 μmol, 1.00 equiv) and 10.0 equiv of olefin 2e (168 mg, 2.00 mmol) were dissolved in degassed, dry CH2Cl2 (c = 20 mM). The reaction solution was irradiated at λ = 419 nm in a Duran tube at r.t., and the reaction progress was monitored by TLC. When no further conversion was observed by TLC (t = 12 h), the reaction was stopped and all volatiles were removed. Purification by column chromatography (pentane/Et2O = 20:1) gave product 3e as a yellow oil (27.5 mg, 118 μmol, 59%). When performed on a mmol scale (150 mg 1), product 3e was obtained in 56% yield (132 mg). 1H NMR (500 MHz, CDCl3, 300 K): δ = 0.71 (s, 3 H, CH3-2), 1.15 (s, 3 H, CH3-3), 1.19 (s, 3 H, CH3-2), 1.24 (s, 3 H, CH3-3), 3.97 (d, 3 J = 10.1 Hz, 1 H, H-1), 4.91 (d, 3 J = 10.1 Hz, 1 H, H-4), 7.08–7.13 (m, 2 H, ortho-HAr), 7.23–7.28 (m, 1 H, para-HAr), 7.30–7.37 (m, 2 H, meta-HAr) ppm. 13C NMR (101 MHz, CDCl3, 300 K): δ = 19.5 (q, CH3-3), 21.5 (q, CH3-2), 22.8 (q, CH3-3), 24.3 (q, CH3-2), 39.3 (s, C-2), 44.9 (s, C-3), 49.4 (d, C-1), 84.9 (d, C-4), 127.0 (ortho-CArH). 127.1 (d, para-CArH), 128.6 (d, meta-CArH), 136.4 (s, CAr) ppm.

      • For thermal [2+2] cycloaddition reactions of trans-β-nitrostyrene (1) and olefins, see:
    • 22a Brannock KC. Bell A. Burpitt RD. Kelly CA. J. Org. Chem. 1964; 29: 801
    • 22b Scheeren HW. Frissen AE. Synthesis 1983; 794
    • 22c Albrecht Ł. Dickmeiss G. Acosta FC. Rodríguez-Escrich C. Davis RL. Jørgensen KA. J. Am. Chem. Soc. 2012; 134: 2543
    • 22d Seebach D. Sun X. Ebert M.-O. Schweizer WB. Purkayastha N. Beck AK. Duschmalé J. Wennemers H. Mukaiyama T. Benohoud M. Hayashi Y. Reiher M. Helv. Chim. Acta 2013; 96: 799
    • 22e Dobi Z. Holczbauer T. Soós T. Eur. J. Org. Chem. 2017; 1391
  • 23 Yan Q. Liu M. Kong D. Zi G. Hou G. Chem. Commun. 2014; 50: 12870
  • 24 Quan X.-J. Ren Z.-H. Wang Y.-Y. Guan Z.-H. Org. Lett. 2014; 16: 5728
  • 25 Keene C. Kürti L. Synthesis 2013; 45: 1719
    • 26a Bluhm AL. Weinstein J. J. Am. Chem. Soc. 1965; 87: 5511
    • 26b Miller DB. Flanagan PW. Shechter H. J. Org. Chem. 1976; 41: 2112
    • 26c Desiraju GR. Pedireddi VR. J. Chem. Soc., Chem. Commun. 1989; 1112
  • 27 The reaction time was 6 h. If the isomerization was performed starting from cis-β-nitrostyrene under otherwise identical conditions, the cis/trans ratio was 82:18.
  • 28 The tabulated triplet energy (ET) of thioxanthone is ET = 265 kJ mol–1: Murov SL. Carmichael I. Hug GL. Handbook of Photochemistry . 2nd ed. Marcel Dekker; New York: 1993: 80
    Google Scholar
  • 29 Xiong H. Foulk M. Aschenbrenner L. Fan J. Tiong-Yip C.-L. Johnson KD. Moustakas D. Fleming PR. Brown DG. Zhang M. Ferguson D. Wu D. Yu Q. Bioorg. Med. Chem. Lett. 2013; 23: 6789
    • 30a Müller F. Mattay J. Chem. Rev. 1993; 93: 99
    • 30b Mori T. Inoue Y. Chem. Soc. Rev. 2013; 42: 8122