OPEN ACCESS | PEER-REVIEWED | RESEARCH ARTICLE | DOWNLOAD PDF | VIEW FULL-TEXT PDF | TOTAL VIEWS
Regiospecific substitution of the β-vinylic sp2 carbon of cyclohexenones bearing the α-chloro- and β-tosylate-groups: Single crystal XRD/Hirshfeld surface/in-silico studies of three representative compounds
Arkalgud Satyanarayana Jeevan Chakravart (1,*) , Suresh Hari Prasad (2)
(1) Department of Studies in Chemistry, Jnana Bharathi Campus, Bangalore University, Bengaluru, 560056, India
(2) Department of Studies in Chemistry, Central College Campus, Bengaluru City University, Bengaluru, 560001, Karnataka, India
(*) Corresponding Author
Received: 11 Aug 2020 | Revised: 14 Sep 2020 | Accepted: 15 Sep 2020 | Published: 31 Dec 2020 | Issue Date: December 2020
2-Chloro-3-tosyl-5,5-dimethyl-2-cyclohexenone was subjected to a series of regiospecific Suzuki-Miyaura cross-coupling reactions in suspensions of nine different substituted boronic acids, Pd(OAc)2, P(Ph3)3, K3PO4 and 1,4-dioxane solvent, under sealed tube conditions. The regiospecific substitution of the tosyl-group by the aryl group in preference over the chloride- group was observed. A comparison between the bromo- and tosylate group’s reactivities is highlighted. Using the methodology, the products: 2-chloro-3-aryl-5,5-dimethyl-2-cyclohexenones were isolated in greater than 85% yields. Good quality crystals of three representative compounds were obtained by slow evaporation technique and subjected to single crystal XRD studies, Hirshfeld surface analysis, 3-D energy framework, and molecular docking studies. Crystal data for compound 3; C15H17ClO4S: monoclinic, space group P21/c (no. 14), a = 8.8687(3) Å, b = 10.5537(4) Å, c = 16.6862(7) Å, β = 89.807(3)°, V = 1561.78(10) Å3, Z = 4, T = 290 K, μ(MoKα) = 0.390 mm-1, Dcalc = 1.398 g/cm3, 13623 reflections measured (6.716° ≤ 2Θ ≤ 54.962°), 3570 unique (Rint = 0.0467, Rsigma = 0.0512) which were used in all calculations. The final R1 was 0.0452 (I > 2σ(I)) and wR2 was 0.1019 (all data). Crystal data for compound 5e; C20H18O2FCl: monoclinic, space group P21/c (no. 14), a = 6.4900(5) Å, b = 18.6070(13) Å, c = 14.2146(11) Å, β = 102.324(2)°, V = 1677.0(2) Å3, Z = 4, T = 296(2) K, μ(MoKα) = 0.239 mm-1, Dcalc = 1.309 g/cm3, 25575 reflections measured (6.262° ≤ 2Θ ≤ 52.224°), 3283 unique (Rint = 0.0494, Rsigma = 0.0307) which were used in all calculations. The final R1 was 0.0875 (I > 2σ(I)) and wR2 was 0.2056 (all data). Crystal data for compound 5h; C12H13OSCl: triclinic, space group P-1 (no. 2), a = 6.7517(6) Å, b = 8.8376(9) Å, c = 12.6049(12) Å, α = 109.538(3)°, β = 98.597(3)°, γ = 90.417(3)°, V = 699.52(12) Å3, Z = 2, T = 290 K, μ(MoKα) = 0.410 mm-1, Dcalc = 1.376 g/cm3, 28754 reflections measured (6.114° ≤ 2Θ ≤ 59.288°), 3898 unique (Rint = 0.0544, Rsigma = 0.0349) which were used in all calculations. The final R1 was 0.1101 (I > 2σ(I)) and wR2 was 0.2481 (all data).
Our editors have decided to support scientists to publish their manuscripts in European Journal of Chemistry without any financial constraints.
1- The article processing fee will not be charged from the articles containing the single-crystal structure characterization between November 15, 2022 and December 28, 2022 (Voucher code: SINGLE2022).
2. Young writers will not be charged for the article processing fee between November 15, 2022 and December 28, 2022 (Voucher code: YOUNG2022).
3. The article processing fee will not be charged from the articles containing a part of the PhD thesis between November 15, 2022 and December 28, 2022 (Voucher code: PhD2022).
4. The article processing fee will not be charged from authors who have at least one publication in the European Journal of Chemistry between November 15, 2022 and December 28, 2022 (Voucher code: (Voucher code: AUTHOR2022).
European Journal of Chemistry
Links for Article
| | | | | |
| | | | | | |
| | | |
Article MetricsThis Abstract was viewed 1107 times | PDF Article downloaded 291 times
The Council of Scientific and Industrial Research (CSIR), SRF – File no. 09/039(0119)/2018-EMR-1, Government of India, New Delhi, INDIA.
. Li, Y.; Luo, Y.; Peng, L.; Li, Y.; Zhao, B.; Wang, W.; Lang, H.; Deng, Y.; Bai, R.; Lan, Y.; Yin, G. Nature Commun. 2020, 11, 417.
. Lee, H. W.; So, C. M.; Yuen, O. Y.; Wong, W. T.; Kwong, F. Y. Org. Chem. Front. 2020, 7, 926-932.
. Keaveney, S. T.; Kundu, G.; Schoenebeck, F. Angew. Chem. Int. Ed. Engl. 2018, 130, 12753-12757.
. Komeyama, K.; Tsunemitsu, R.; Michiyuki, T.; Yoshida, H.; Osaka, I. Molecules 2019, 24, 1458-1468.
. Chakravarthy, A. S. J.; Pavan, K. P.; Venkatesh, G. B.; Hariprasad, S. Synthetic Commun. 2020, 50(6), 849-857.
. Chakravarthy, A. S. J.; Madhura, M. J.; Gayathri, V.; Hariprasad, S. Tetrahedron Lett. 2020, 60(2), 151391.
. Chakravarthy, A. S. J.; Krishnamurthy, M. S.; Begum, N. S.; Hariprasad, S. Mol. Crys. Liq. Crys. 2019, 682(1), 65-76.
. APEX2 Bruker, SAINT-Plus and SADABS, Bruker AXS Inc., Wisconsin, Madison, USA, 2004.
. Sheldrick, G. M. Acta Cryst. C, 2015, 71, 3-8.
. Spek, A. L. Acta Cryst. C 2015, 71, 9-18.
. Macrae, C. F.; Bruno, I. J.; Chisholm, J. A.; Edgington, P. R.; McCabe, P.; Pidcock, E.; Rodriguez-Monge, L.; Taylor, R.; van de Streek, J.; Wood. P. A. J. Appl. Cryst. 2008, 41(2), 466-470.
. Sreenatha, N. R.; Lakshminarayana, B. N.; Ganesha, D. P.; Gnanendra, C. R. Acta Cryst. E 2018, 74, 1451-1454.
. Sreenatha, N. R.; Lakshminarayana, B. N.; Ganesha, D. P.; Vijayshankar, S.; Nagaraju, S. X-Ray Struc. Anal. Online 2018, 34, 24-25.
. Spackman, M. A.; Jayatilaka, D. Cryst. Eng. Comm. 2009, 11, 19-32.
. Spackman, M. A.; McKinnon, J. J.; Jayatilaka, D. Cryst. Eng. Comm. 2008, 10(4), 377-388.
. McKinnon, J. J.; Jayatilaka, D.; Spackman, M. A. Chem. Comm. 2017, 3814-3816.
. Turner, M. J.; McKinnon, J. J.; Wolff, S. K.; Grimwood, D. J.; Spackman, P. R.; Jayatilaka, D.; Spackman, M. A. CrystalExplorer 17.5. The University of Western Australia, 2017.
. Turner, M. J.; Grabowsky, S.; Jayatilaka, D.; Spackman, M. A. J. Phys. Chem. Lett. 2014, 5, 4249-4255.
. Sanner, M. F. J. Mol. Grap. Mod. 1999, 17(1), 57-61.
. Wallace, A. C.; Laskowski, R. A.; Thornton, J. M. Prot. Eng. 1995, 8(2), 127-134.
. McVeigh, M. S.; Kelleghan, A. V.; Yamano, M. M.; Knapp, R. R.; Garg, N. K. Org. Lett. 2020, 22(11), 4500-4504.
. Geenen, S. R.; Schumann, T.; Mueller, T. J. J. J. Org. Chem. 2020, 85(15), 9737-9750.
. Mpungose, P. P.; Vundla, Z. P.; Maguire, G. E. M.; Friedrich, H. B. Molecules 2018, 23(7), 1676-1699.
. Boeyens, J. C. A. J. Cryst. Mol. Struct. 1978, 8, 317-320.
. Cremer, D. Acta Cryst. B 1984, 40, 498-500.
. Sreenatha, N. R.; Chakravarthy, A. S. J.; Suchithra, B.; Lakshminarayana, B. N.; Hariprasad, S.; Ganesha, D. P. J. Mol. Struc. 2020, 1210, 127979.
. Sreenatha, N. R.; Chakravarthy, A. S. J.; Lakshminarayana, B. N.; Hariprasad, S. J. Mol. Struc. 2021, 1225, 129116.
. Sreenatha, N. R.; Lakshminarayana, B. N.; Ganesha, D. P.; Gnanendra, C. R.; Nagaraju, S.; Madan, S. K. Chem. Data Coll. 2018, 17-18, 394-403.
. Sreenatha, N. R.; Lakshminarayana, B. N.; Madan, S. K.; Mahadeva, T. N. P.; Kiran, K. S.; Vijayshankar, D, S.; Byrappa, K. Chem. Data Coll. 2017, 11-12, 131-138.
. Mackenzie, C. F.; Spackman, P. R.; Jayatilaka, D.; Spackman, M. A. IUCrJ 2017, 4(5), 575-587.
. Gysin, S. Genes Cancer 2011, 2(3), 359-372.
. O'Bryan, J. P. Pharmacol Res. 2019, 139, 503-511.
. Janes, M. R.; Zhang, J.; Li, L. Cell 2018, 172(3), 578-589.e17.
The Supplementary Material for this article can be found online at: Supplementary files
How to cite
The other citation formats (EndNote | Reference Manager | ProCite | BibTeX | RefWorks) for this article can be found online at: How to cite item
DOI Link: https://doi.org/10.5155/eurjchem.11.4.261-275.2020
| | | | | | | |
| | | | | | |
Save to Zotero Save to Mendeley
European Journal of Chemistry 2020, 11(4), 261-275 | doi: https://doi.org/10.5155/eurjchem.11.4.261-275.2020 | Get rights and content
- There are currently no refbacks.
Copyright (c) 2020 Authors
This work is published and licensed by Atlanta Publishing House LLC, Atlanta, GA, USA. The full terms of this license are available at http://www.eurjchem.com/index.php/eurjchem/pages/view/terms and incorporate the Creative Commons Attribution-Non Commercial (CC BY NC) (International, v4.0) License (http://creativecommons.org/licenses/by-nc/4.0). By accessing the work, you hereby accept the Terms. This is an open access article distributed under the terms and conditions of the CC BY NC License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited without any further permission from Atlanta Publishing House LLC (European Journal of Chemistry). No use, distribution or reproduction is permitted which does not comply with these terms. Permissions for commercial use of this work beyond the scope of the License (http://www.eurjchem.com/index.php/eurjchem/pages/view/terms) are administered by Atlanta Publishing House LLC (European Journal of Chemistry).
© Copyright 2010 - 2022 • Atlanta Publishing House LLC • All Right Reserved.
The opinions expressed in all articles published in European Journal of Chemistry are those of the specific author(s), and do not necessarily reflect the views of Atlanta Publishing House LLC, or European Journal of Chemistry, or any of its employees.
Copyright 2010-2022 Atlanta Publishing House LLC. All rights reserved. This site is owned and operated by Atlanta Publishing House LLC whose registered office is 2850 Smith Ridge Trce Peachtree Cor GA 30071-2636, USA. Registered in USA.