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Pure and Applied Chemistry

The Scientific Journal of IUPAC

Ed. by Burrows, Hugh / Stohner, Jürgen

IMPACT FACTOR 2017: 5.294

CiteScore 2017: 3.42

SCImago Journal Rank (SJR) 2017: 1.212
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Volume 89, Issue 6


Light guided chemoselective olefin metathesis reactions

Ofer Reany / N. Gabriel Lemcoff
Published Online: 2017-03-17 | DOI: https://doi.org/10.1515/pac-2016-1221


An appealing concept in synthetic chemistry is photo-induced catalysis; where dormant complexes become catalytically active upon activation with light. The ruthenium-based olefin metathesis complexes founded on the original Grubbs catalyst have probably been one of the most widely studied families of catalysts for the past 25 years. Greater stability and versatility of these olefin-metathesis catalysts has been achieved by careful design of the ligand sphere, including latent catalysts which are activated by external stimuli. This article describes our recent developments towards light-induced olefin metathesis reactions based on photoactive sulfur-chelated ruthenium benzylidene catalysts. Alternative chemical reactions, be it photo-induced olefin metathesis or other direct photochemical processes, by using light of different frequencies were studied in chemoselective chromatic orthogonal pathways. The lessons learned during the development of these reactions have given birth to selective photo-deprotection sequences and novel pathways for stereolithographic applications.

Keywords: chromatic orthogonality; ICPOC-23; latent catalysts; olefin metathesis; photochemistry; ruthenium complexes

Article note:

A collection of invited papers based on a presentations at the 23rd International Conference on Physical Organic Chemistry (ICPOC-23), Sydney, Australia, 3–8 July, 2016.


  • [1]

    Y. Chauvin. Angew. Chem. Int. Ed. 45, 3740 (2006).CrossrefGoogle Scholar

  • [2]

    R. R. Schrock. Angew. Chem. Int. Ed. 45, 3748 (2006).CrossrefGoogle Scholar

  • [3]

    R. H. Grubbs. Angew. Chem. Int. Ed. 45, 3760 (2006).CrossrefGoogle Scholar

  • [4]

    S. Kress, S. Blechert. Chem Soc. Rev. 41, 4389 (2012).CrossrefGoogle Scholar

  • [5]

    D. J. Nelson, S. Manzini, C. A. Urbina-Blanco, S. P. Nolan. Chem. Commun. 50, 10355 (2014).CrossrefGoogle Scholar

  • [6]

    A. H. Hoveyda. J. Org. Chem. 79, 4763 (2014).CrossrefGoogle Scholar

  • [7]

    I. C. Stewart, C. J. Douglas, R. H. Grubbs. Org. Lett. 10, 441 (2008).CrossrefGoogle Scholar

  • [8]

    Y. Liang, R. Raju, T. Le, C. D. Taylor, A. R. Howell. Tet. Lett. 50, 1020 (2009).CrossrefGoogle Scholar

  • [9]

    T. Vorfalt, S. Leuthuer, H. t Plenio. Angew Chem. Int. Ed. 48, 5191 (2009).CrossrefGoogle Scholar

  • [10]

    Hejl, M. W. Day, R. H. Grubbs. Organometallics 25, 6149 (2006).CrossrefGoogle Scholar

  • [11]

    A. Szadkowska, K. Grela. Curr. Org. Chem. 12, 1631 (2008).CrossrefGoogle Scholar

  • [12]

    S. Monsaert, A. L. Vila, R. Drozdzak, P. Van Der Voort, F. Verpoort, Chem. Soc. Rev. 38, 3360 (2009).CrossrefGoogle Scholar

  • [13]

    A. Szadkowska, X. Gstrein, D. Burtscher, K. Jarzembska, K. Wozniak, C. Slugovc, K. Grela, Organometallics 29, 117 (2010).CrossrefGoogle Scholar

  • [14]

    J. S. M. Samec, B. K. Keitz, R. H. Grubbs J. Organometallic Chem. 695, 1831 (2010).CrossrefGoogle Scholar

  • [15]

    C. E. Diesendruck, O. Ilyashevsky, A. Ben-Asuly, I. Goldberg, B. N. G. Lemcoff. Macromol. Symp. 293, 33 (2010).CrossrefGoogle Scholar

  • [16]

    D. M. Hudson, E. J. Valente, J. Schachner, M. Limbach, K. Muller, H.-J. Schanz. ChemCatChem 3, 297 (2011).CrossrefGoogle Scholar

  • [17]

    R. M. Thomas, A. Fedorov, B. K. Keitz, R. H. Grubbs. Organometallics 30, 6713 (2011).CrossrefGoogle Scholar

  • [18]

    R. T. M. Jakobs, R. P. Sijbesma. Organometallics 31, 2476 (2012).CrossrefGoogle Scholar

  • [19]

    A. Leitgeb, M. Abbas, R. C. Fischer, A. Poater, L. Cavalloef, C. Slugovc. Catal. Sci. Tech. 2, 1640 (2012).CrossrefGoogle Scholar

  • [20]

    M. Rouen, P. Queval, L. Falivene, J. Allard, L. Toupet, C. e Crvisy, F. Caijo, O. Basl, L. Cavallo, M. Mauduit. Chem. Eur. J. 20, 13716 (2014).CrossrefGoogle Scholar

  • [21]

    B. Ö. Öztürk, S. K. Sehitoglu, M. A. R. Meier. Eur. Polym. J. 62, 116 (2015).CrossrefGoogle Scholar

  • [22]

    K. Żukowska, E. Pump, A. E. Pazio, K. Woźniak, L. Cavallo, C. Slugovc. Beilstein J. Org. Chem. 11, 1458 (2015).CrossrefGoogle Scholar

  • [23]

    R. Drozdzak, N. Nishioka, G. Recher, F. Verpoort. Macromol. Symp. 293, 1 (2010).CrossrefGoogle Scholar

  • [24]

    For a review on sulfur-chelated benzylidene complexes see: Y. Vidavsky, A. Anaby, N. G. Lemcoff. Dalton Trans 41, 32 (2012).CrossrefGoogle Scholar

  • [25]

    E. Tzur, G. Lemcoff in Handbook of Metathesis Vol. 3: Polymer Synthesis. R. H. Grubbs, E. Khorsavi (Eds.), Wiley-VCH, Chap. 12 (2012).Google Scholar

  • [26]

    P. A. Van der Schaaf, R. Kolly, H.-J. Kirner, F. Rime, A. Muhlebach, A. Hafner. J. Organomet. Chem. 606, 65 (2000).CrossrefGoogle Scholar

  • [27]

    T. Ung, A. Hejl, R. H. Grubbs, Y. Schrodi. Organometallics 23, 5399 (2004).CrossrefGoogle Scholar

  • [28]

    A. Ben-Asuly, E. Tzur, C. E. Diesendruck, M. Sigalov, I. Goldberg, N. G. Lemcoff. Organometallics 27, 811 (2008).CrossrefGoogle Scholar

  • [29]

    T. Kost, M. Sigalov, I. Goldberg, A. Ben-Asuly, N. G. Lemcoff. J. Organomet. Chem. 693, 2200 (2008).CrossrefGoogle Scholar

  • [30]

    C. E. Diesendruck, Y. Vidavsky, A. Ben-Asuly, N. G. Lemcoff. J. Polym. Sci. A Polym. Chem. 47, 4209, (2009).CrossrefGoogle Scholar

  • [31]

    C. E. Diesendruck, E. Tzur, A. Ben-Asuly, I. Goldberg, B. F. Straub, N. G. Lemcoff. Inorg. Chem. 48, 0819 (2009).CrossrefGoogle Scholar

  • [32]

    E. Tzur, A. Szadkowska, A. Ben-Asuly, A. Makal, I. Goldberg, K. Wozniak, K. Grela, N. G. Lemcoff. Chem. Eur. J. 16, 8726 (2010).CrossrefGoogle Scholar

  • [33]

    A. Aharoni, Y. Vidavsky, C. E. Diesendruck, A. Ben-Asuly, I. Goldberg, N. G. Lemcoff. Organometallics 30, 1607 (2011).CrossrefGoogle Scholar

  • [34]

    Y. Ginzburg, A. Anaby, Y. Vidavsky, C. E. Diesendruck, A. Ben-Asuly, I. Goldberg, N. G. Lemcoff. Organometallics 30, 3430 (2011).CrossrefGoogle Scholar

  • [35]

    O. Ablialimov, M. Kędziorek, M. Malińska, K. Woźniak, K. Grela. Organometallics 33, 2160 (2014).CrossrefGoogle Scholar

  • [36]

    K. Grudzien, K. Zukowska, M. K. Wozniak, M. Barbasiewicz. Chem-Eur. J. 20, 2819 (2014).CrossrefGoogle Scholar

  • [37]

    B. Bieszczad, M. Barbasiewicz. Chem. Eur. J. 21, 10322 (2015).CrossrefGoogle Scholar

  • [38]

    E. Pump, L. Cavallo, C. Slugovc. Monatsh. Chem. 146, 1131 (2015).CrossrefGoogle Scholar

  • [39]

    M. S. Mikus, S. Torker, C. Xu, B. Li, A. H. Hoveyda. Organometallics 35, 3878 (2016).CrossrefGoogle Scholar

  • [40]

    B. K. Keitz, R. H. Grubbs. J. Am. Chem. Soc. 131, 2038 (2009).CrossrefGoogle Scholar

  • [41]

    S. J. Pastine, D. Okawa, A. Zettl, J. M. J. Fre’chet. J. Am. Chem. Soc. 131, 13586 (2009).CrossrefGoogle Scholar

  • [42]

    D. Wang, K. Wurst, M. R. Buchmeiser. Chem. Eur. J. 16, 12928 (2010).CrossrefGoogle Scholar

  • [43]

    D. Wang, J. Unold, M. Bubrin, W. Frey, W. Kaim, M. R. Buchmeiser. ChemCatChem 4, 1808 (2012).CrossrefGoogle Scholar

  • [44]

    D. Wang, J. Unold, M. Bubrin, I. Elser, W. Frey, W. Kaim, G. Xu, M. R. Buchmeiser. Eur. J. Inorg. Chem. 2013, 5462 (2013).CrossrefGoogle Scholar

  • [45]

    Y. Vidavsky, N. G. Lemcoff. Beilstein J. Org. Chem. 6, 1106 (2010).CrossrefGoogle Scholar

  • [46]

    R. Stoll, S. Hecht, Angew. Chem. Int. Ed. 49, 5054 (2010).CrossrefGoogle Scholar

  • [47]

    Y. Zhang, D. Wang, P. Lonnecke, T. Scherzer, M. R. Buchmeiser. Macromol. Symp. 236, 30 (2006).CrossrefGoogle Scholar

  • [48]

    R. A. Weitekamp, H. A. Atwater, R. H. Grubbs. J. Am. Chem. Soc. 135, 16817 (2013).CrossrefGoogle Scholar

  • [49]

    A. Ben-Asuly, A. Aharoni, C. E. Diesendruck, Y. Vidavsky, I. Goldberg, B. F. Straub, N. G. Lemcoff. Organometallics 28, 4652 (2009).CrossrefGoogle Scholar

  • [50]

    E. Levin, S. Mavila, O. Eivgi, E. Tzur, N. G. Lemcoff. Angew Chem. Int. Ed. 54, 12384 (2015).CrossrefGoogle Scholar

  • [51]

    R. L. Sutar, E. Levin, D. Butilkov, I. Goldberg, O. Reany, N. G. Lemcoff. Angew Chem. Int. Ed. 55, 764 (2016).CrossrefGoogle Scholar

  • [52]

    E. Alessio, G. Mestroni, G. Nardin, W. M. Attia, M. Calligaris, G. Sava, S. Zorzet. Inorg. Chem. 27, 4099 (1998).Google Scholar

  • [53]

    T. G. Appleton, H. C. Clark, L. E. Manzer. Coord. Chem. Rev. 10, 335 (1973).CrossrefGoogle Scholar

  • [54]

    J. C. Toledo, B. S. L. Neto, D. W. Franco. Coord. Chem. Rev. 249, 419 (2005).CrossrefGoogle Scholar

  • [55]

    For extensive discussion on trans influence in chelating alkylidene ligands see ref. 28.Google Scholar

  • [56]

    M. Barbasiewicz, A. Szadkowska, R. Bujok, K. Grela. Organometallics 25, 3599 (2006).CrossrefGoogle Scholar

  • [57]

    C. G. Bochet. Angew. Chem. Int. Ed. 40, 2071 (2001).CrossrefGoogle Scholar

  • [58]

    For review on phtotoremovable protecting groups in chemistry and biology see: P. Klan, T. Solomek, C. G. Bochet, A. Blanc, R. Givens, M. Rubina, V. Popik, A. Kostikov, J. Wirz. Chem. Rev. 113, 119 (2013).CrossrefGoogle Scholar

  • [59]

    C. G. Bochet. Tetrahedron Lett. 41, 6341 (2000).CrossrefGoogle Scholar

  • [60]

    A. Blanc, C. G. Bochet. Org. Lett. 9, 2649 (2009).Google Scholar

  • [61]

    V. San Miguel, C. G. Bochet, A. del Campo. J. Am. Chem. Soc. 133, 5380 (2011).CrossrefGoogle Scholar

  • [62]

    For examples related to biochemistry see: C. Brieke, F. Rohrbach, A. Gottschalk, G. Mayer, A. Heckel. Angew. Chem. Int. Ed. 51, 8446 (2012).CrossrefGoogle Scholar

  • [63]

    P. Klan, T. Solomek, C. G. Bochet, A. Blanc, R. Givens, M. Rubina, V. Popik, A. Kostikov, J. Wirz. Chem Rev. 113, 119 (2013).CrossrefGoogle Scholar

  • [64]

    A. Blanc, C. G. Bochet. J. Org. Chem. 67, 5567 (2002).CrossrefGoogle Scholar

  • [65]

    C. G. Bochet. Synlett 13, 2268 (2004).Google Scholar

  • [66]

    M. J. Hansen, W. A. Velema, M. M. Lerch, W. Szymanski, B. L. Feringa. Chem. Soc. Rev. 44, 3358 (2015).CrossrefGoogle Scholar

  • [67]

    M. A. Brook, C. Gottardo, S. Balduzzi, M. Mohamed. Tetrahedron Lett. 38, 6997 (1997).CrossrefGoogle Scholar

  • [68]

    M. S. Taylor, E. N. Jacobsen. PNAS 101, 5368 (2004).CrossrefGoogle Scholar

  • [69]

    C.-H. Wong, S. C. Zimmerman. Chem. Commun. 49, 1679 (2013).CrossrefGoogle Scholar

  • [70]

    F. Zhang, D. R. Spring. Chem. Soc. Rev. 43, 6906 (2014).CrossrefGoogle Scholar

  • [71]

    S. Liao, X.-L. Sun, Y. Tang. Acc. Chem. Res. 47, 2260 (2014).CrossrefGoogle Scholar

  • [72]

    H. Sung, Y. Huang. Synlett 26, 2751 (2015).CrossrefGoogle Scholar

  • [73]

    C. G. Frost, P. Marce, P. M. Liu. Organomet. Chem. 40, 54 (2016).Google Scholar

  • [74]

    B. Schmidt, S. Nave. Chem Commun. 2489 (2006).Google Scholar

  • [75]

    B. Schmidt, S. Nave. Adv. Synth. Catal. 349, 215 (2007).CrossrefGoogle Scholar

  • [76]

    For studies on ring size-selectivity in RCM see: M. B. Dinger, J. C. Mol. Organometallics 22, 1089 (2003) and Ref. 77–81.CrossrefGoogle Scholar

  • [77]

    T. M. Trnka, J. P. Morgan, M. S. Sanford, T. E. Wilhelm, M. Scholl, T.-L. Choi, S. Ding, M. W. Day, R. H. Grubbs. J. Am. Chem. Soc. 125, 2546 (2003).CrossrefGoogle Scholar

  • [78]

    B. Schmidt. Synlett 2004, 1541 (2004).Google Scholar

  • [79]

    S. Michaelis, S. Blechert. Org. Lett. 7, 5513 (2005).CrossrefGoogle Scholar

  • [80]

    N. J. Beach, K. D. Camm, D. E. Fogg. Organometallics 29, 5450 (2010).CrossrefGoogle Scholar

  • [81]

    K. Yoshida, Y. Kano, H. Takahashi, A. Yanagisawa. Adv. Synth. Catal. 353, 1229 (2011).CrossrefGoogle Scholar

  • [82]

    H. Ito, C. G. Willson. in Polymers in Electronics. T. Davidson (Ed.), ACS Symposium Series, 242; ACS Publications: Washington, DC, pp 11–23 (1984).Google Scholar

  • [83]

    R. F. Harris, M. J. Ricci, R. A. Farrer, J. Praino, S. J. Miller, B. E. A; Saleh, M. C; Teich, J. T Fourkas. Adv. Mater. 17, 39 (2005).CrossrefGoogle Scholar

  • [84]

    M. B. Dinger, P. Nieczypor, J. C. Mol. Organometallics 22, 5291 (2003).CrossrefGoogle Scholar

  • [85]

    M. Süßner, H. Plenio. Chem. Commun. 5417 (2005).Google Scholar

  • [86]

    S. Leuthäuβer, V. Schmidts, C. M. Thiele, H. Plenio, Chem. Eur. J. 14, 5465 (2008).CrossrefGoogle Scholar

  • [87]

    S. Manzini, C. A. Urbina-Blanco, D. J. Nelson, A. Poater, T. Lebl, S. Meiries, A. M. Z Slawin, L. Falivene, L. Cavallo, S. P. Nolan. J. Organomet. Chem. 2015, 780, 43 (2015).Google Scholar

  • [88]

    M. B. Herbert, B. A. Suslick, P. Liu, L. Zou, P. K. Dornan, K. N. Houk, R. H. Grubbs. Organometallics 34, 2858 (2015).CrossrefGoogle Scholar

  • [89]

    For a recent review on latent polymerization, including metathesis polymers see: S. Naumann, M. R. Buchmeiser. Macromol. Rapid Commun. 35, 682 (2014).CrossrefGoogle Scholar

  • [90]

    The coinage of the term PROMP was introduced by P. A. van der Schaaf, A. Hafner, A. Mühlebach. Angew. Chem. Int. Ed. 35, 1845 (1996).CrossrefGoogle Scholar

  • [91]

    A. Hafner, A. Mühlebach, P. A. van der Schaaf. Angew. Chem. Int. Ed. 36, 2121 (1997).CrossrefGoogle Scholar

About the article

Published Online: 2017-03-17

Published in Print: 2017-06-27

Citation Information: Pure and Applied Chemistry, Volume 89, Issue 6, Pages 829–840, ISSN (Online) 1365-3075, ISSN (Print) 0033-4545, DOI: https://doi.org/10.1515/pac-2016-1221.

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