Abstract
There is increased evidence that the effect of bulky groups in organic, organometallic, and inorganic chemistry is not only repulsive but can be attractive because of London dispersion interactions. The influence of the size of primary alkyl substituents in 2- and 2,3-positions of anthracenes on the diastereoselectivity (anti vs syn dimer) of the [π4s + π4s] photoinduced dimerization is investigated. The synthesis of the anthracene derivatives was achieved by Suzuki-Miyaura reaction of 2,3-dibromoanthracene with alkylboronic acids as well as by reduction of anthraquinones that were obtained from 2,3-disubstituted 1,3-butadienes and naphthoquinone followed by dehydrogenation. The mixtures of dianthracene isomers were analyzed with respect to the anti/syn-ratio of the products by X-ray crystallography and nuclear Overhauser effect spectroscopy. While for the 2,3-dimethylanthracene the anti and syn isomers were formed in equal amounts, the anti dimers are the major products in all other cases. A linear correlation (R2 = 0.98) between the steric size (Charton parameter) and the isomeric ratio suggests that the selectivity is dominated by classical repulsive steric effects. An exception is the iso-butyl substituent that produces an ...Continue Reading
References
Dec 12, 2000·Organic Letters·G P Miller, J Mack
Aug 5, 1997·Chemical Reviews·Jennifer C. Ma, Dennis A. Dougherty
May 13, 2003·Chemistry : a European Journal·Chérif F MattaRichard F W Bader
Apr 24, 2004·The Journal of Organic Chemistry·Oscar NavarroSteven P Nolan
Jun 2, 2006·Organic Letters·Francesco FringuelliLuigi Vaccaro
Jul 15, 2006·The Journal of Organic Chemistry·David Bailey, Vance E Williams
Nov 8, 2008·Physical Chemistry Chemical Physics : PCCP·Jeng-Da Chai, Martin Head-Gordon
Mar 20, 2010·Angewandte Chemie·Fabien Durola, Julius Rebek
Apr 29, 2010·The Journal of Chemical Physics·Stefan GrimmeHelge Krieg
Nov 26, 2010·Chemical Communications : Chem Comm·Haruo AikawaMasahiko Yamaguchi
Jun 16, 2012·Physical Chemistry Chemical Physics : PCCP·Balazs PinterFrank De Proft
Dec 12, 2012·Accounts of Chemical Research·Dennis A Dougherty
Apr 17, 2014·Organic Letters·Christoph SämannPaul Knochel
Sep 17, 2014·Journal of the American Chemical Society·Ling LiMark R Biscoe
Jan 30, 2015·Angewandte Chemie·Chengxi LiWenjun Tang
Aug 12, 2015·Angewandte Chemie·J Philipp Wagner, Peter R Schreiner
Aug 22, 2017·Journal of the American Chemical Society·Robert PollicePeter Chen
Oct 27, 2017·The Journal of Physical Chemistry. a·Ali MirchiJerzy Leszczynski
Aug 3, 2018·Chemistry : a European Journal·Marta Marin-LunaHendrik Zipse
Oct 13, 2018·Chemical Science·Marta Marin-LunaHendrik Zipse
Dec 27, 2018·Accounts of Chemical Research·Markus BurschStefan Grimme
Citations
Jan 28, 2020·Chemistry : a European Journal·Thomas GeigerHolger F Bettinger
Mar 1, 2020·Israel Journal of Chemistry·Doleshwar NiroulaRamesh Giri
Jun 8, 2021·Chemical Science·Guowei ZhangLei Zhang
Jul 2, 2021·Journal of the American Chemical Society·Takashi IkawaShuji Akai
Aug 31, 2021·Beilstein Journal of Organic Chemistry·Giovanni S Baviera, Paulo M Donate