Rhodium catalysts with superbulky NHC ligands for the selective α-hydrothiolation of alkynes.

[en] Eight rhodium complexes-including four new compounds-with the generic formula [RhCl(cod)(NHC)] (cod is 1,3-cyclooctadiene) differing by the size of their N-heterocyclic carbene (NHC) ligand were prepared, characterized, and found to be catalytically active in the hydrothiolation of terminal alkynes with aliphatic or aromatic thiols. The steric bulk of the carbene was found to markedly influence the reaction rate and selectivity. In particular, superbulky NHCs led to the almost quantitative formation of the sole α-vinyl sulfide products. The experimental conditions were optimized to allow the straightforward synthesis of a broad range of mono- and disubstituted α-adducts starting from terminal alkynes (18 examples) and thiols (5 examples). Altogether, the procedure devised in this study provides an easy access to α-vinyl sulfides with full atom economy and a low catalyst loading.

Disciplines :

Chemistry

Author, co-author :

Bołt, Małgorzata ; Department of Organometallic Chemistry, Faculty of Chemistry, Adam Mickiewicz University in Poznan, Umultowska 89B, 61-614 Poznan, Poland. pkw@amu.edu.pl

Delaude, Lionel ; Université de Liège - ULiège > Molecular Systems (MolSys)

Żak, Patrycja ; Department of Organometallic Chemistry, Faculty of Chemistry, Adam Mickiewicz University in Poznan, Umultowska 89B, 61-614 Poznan, Poland. pkw@amu.edu.pl

Language :

English

Title :

Rhodium catalysts with superbulky NHC ligands for the selective α-hydrothiolation of alkynes.

Publication date :

15 March 2022

Journal title :

Dalton Transactions

ISSN :

1477-9226

eISSN :

1477-9234

Publisher :

Royal Society of Chemistry, England

Volume :

Issue :

Pages :

4429-4434

Peer reviewed :

Peer reviewed

Additional URL :

http://pubs.rsc.org/en/content/articlepdf/2022/DT/D2DT00243D

Funders :

NCN - Narodowe Centrum Nauki

Funding text :

The authors gratefully acknowledge the financial support from the National Science Centre (Poland) (SONATA Project No. UMO-2016/23/D/ST5/00417).

Available on ORBi :

since 12 April 2022

Statistics

Number of views

59 (4 by ULiège)

Number of downloads

3 (2 by ULiège)

More statistics

Scopus citations^®

Scopus citations^®
without self-citations

OpenCitations

OpenAlex citations

Bibliography

Trost B. M. Lavoie A. C. J. Am. Chem. Soc. 1983 105 5075 5090 10.1021/ja00353a037
Mizuno H. Domon K. Masuya K. Tanino K. Kuwajima I. J. Org. Chem. 1999 64 2648 2656 10.1021/jo981478c 11674332
Sabarre A. Love J. A. Org. Lett. 2008 10 3941 3944 10.1021/ol8012843 18702501
Quinet C. Sampoux L. Markó I. E. Eur. J. Org. Chem. 2009 1806 1811 10.1002/ejoc.200900009
Zhu Y. Xie M. Dong S. Zhao X. Lin L. Liu X. Feng X. Chem. - Eur. J. 2011 17 8202 8208 10.1002/chem.201100520 21647990
Braun M.-G. Zard S. Z. Org. Lett. 2011 13 776 779 10.1021/ol103044x 21244049
Jin W. Du W. Yang Q. Yu H. Chen J. Yu Z. Org. Lett. 2011 13 4272 4275 10.1021/ol201620g 21761823
Cui Y. Floreancig P. E. Org. Lett. 2012 14 1720 1723 10.1021/ol3002877 22420412
Miyamoto K. Hirobe M. Uchiyama M. Ochiai M. Chem. Commun. 2015 51 7962 7965 10.1039/C5CC02000J 25864535
Abiko Y. Matsumura A. Nakabayashi K. Mori H. React. Funct. Polym. 2015 93 170 177 10.1016/j.reactfunctpolym.2015.06.014
Nakabayashi K. Matsumura A. Abiko Y. Mori H. Macromolecules 2016 49 1616 1629 10.1021/acs.macromol.5b02573
Ceruti M. Balliano G. Rocco F. Milla P. Arpicco S. Cattel L. Viola F. Lipids 2001 36 629 636 10.1007/s11745-001-0767-8 11485168
Johannesson P. Lindeberg G. Johansson A. Nikiforovich G. V. Gogoll A. Synnergren B. LeGrèves M. Nyberg F. Karlén A. Hallberg A. J. Med. Chem. 2002 45 1767 1777 10.1021/jm011063a 11960488
Pallela V. R. Mallireddigari M. R. Cosenza S. C. Akula B. Venkata Subbaiah D. R. C. Reddy E. P. Reddy M. V. R. Org. Biomol. Chem. 2013 11 1964 1977 10.1039/C3OB27220F 23386308
Tian Y. Li J. Zeng X. Wang D. Liu Q. Niu X. Huang X. Xu N. Li Z. Chem. Sci. 2016 7 3325 3330 10.1039/C6SC00106H 29997825
(a) Paris J. M., Barriere J. C., Smith C. and Bost P. E., in Recent Progress in the Chemical Synthesis of Antibiotics, ed. G. Lucas and M. Ohno, Springer-Verlag, Berlin, 1990, pp. 182-248 Asano T. Adachi Y. J. Vet. Med. Sci. 2006 68 555 560 10.1292/jvms.68.555 16820711
Hosoda K. Koyama N. Kanamoto A. Tomoda H. Molecules 2019 24 1495 10.3390/molecules24081495 30995807
Dondoni A. Marra A. Eur. J. Org. Chem. 2014 3955 3969 10.1002/ejoc.201301879
Yang Y. Rioux R. M. Green Chem. 2014 16 3916 3925 10.1039/C4GC00642A
Degtyareva E. S. Burykina J. V. Fakhrutdinov A. N. Gordeev E. G. Khrustalev V. N. Ananikov V. P. ACS Catal. 2015 5 7208 7213 10.1021/acscatal.5b01815
Modem S. Kankala S. Balaboina R. Thirukovela N. S. Jonnalagadda S. B. Vadde R. Vasam C. S. Eur. J. Org. Chem. 2016 4635 4642 10.1002/ejoc.201600809
Di Giuseppe A., Castarlenas R. and Oro L. A., in: Rhodium Catalysis, ed. C. Claver, Top. Organomet. Chem., Springer, Berlin, 2018, Vol. 61, pp. 31-67
Yang J. Sabarre A. Fraser L. R. Patrick B. O. Love J. A. J. Org. Chem. 2009 74 182 187 10.1021/jo801644s 19053611
Kankala S. Nerella S. Vadde R. Vasam C. S. RSC Adv. 2013 3 23582 23588 10.1039/C3RA44499F
Palacios L. Artigas M. J. Polo V. Lahoz F. J. Castarlenas R. Pérez-Torennte J. J. Oro L. A. ACS Catal. 2013 3 2910 2919 10.1021/cs400739y
Palacios L. Meheut Y. Galiana-Cameo M. Artigas M. J. Di Giuseppe A. Lahoz F. J. Polo V. Castarlenas R. Pérez-Torennte J. J. Oro L. A. Organometallics 2017 36 2198 2207 10.1021/acs.organomet.7b00251
Seayad A. M. Selvakumar K. Ahmed M. Beller M. Tetrahedron Lett. 2003 44 1679 1683 10.1016/S0040-4039(03)00008-X
Lee S. I. Park S. Y. Park J. H. Jung I. G. Choi S. Y. Chung Y. K. Lee B. Y. J. Org. Chem. 2006 71 91 96 10.1021/jo051685u 16388622
Yu X.-Y. Patrick B. O. James B. R. Organometallics 2006 25 2359 2363 10.1021/om060030w
Berthon-Gelloz G. Siegler M. A. Spek A. L. Tinant B. Reek J. N. H. Markó I. E. Dalton Trans. 2010 39 1444 1446 10.1039/B921894G 20104298
Meiries S. Speck K. Cordes D. B. Slawin A. M. Z. Nolan S. P. Organometallics 2012 32 330 339 10.1021/om3011867
Bołt M. Żak P. Inorg. Chem. 2021 60 17579 17585 10.1021/acs.inorgchem.1c02160 34739755
Dierick C. S. Dewez D. F. Markó I. E. Organometallics 2014 33 677 683 10.1021/om4008955
Savka R. Plenio H. Dalton Trans. 2015 44 891 893 10.1039/C4DT03449J 25437103
Shaw P. Kennedy A. R. Nelson D. J. Dalton Trans. 2016 45 11772 11780 10.1039/C6DT02100J 27335266
Galardon E. Ramdeehul S. Brown J. M. Cowley A. Hii K. K. Jutand A. Angew. Chem., Int. Ed. 2002 41 1760 1763 10.1002/1521-3773(20020517)41:10<1760::AID-ANIE1760>3.0.CO;2-3
Altenhoff G. Goddard R. Lehmann C. W. Glorius F. Angew. Chem., Int. Ed. 2003 42 3690 3693 10.1002/anie.200351325 12916049
Hans M. Lorkowski J. Demonceau A. Delaude L. Beilstein J. Org. Chem. 2015 11 2318 2325 10.3762/bjoc.11.252 26734080 (b) Azap C., Wolf D., Abbenhuis L. H. C., Gerritsen G., Grela K., Wilting J., Leszczyńska K., Czaban J. and Wojtasiewicz A., EP 2368894A1, 2011