Dienylation of Unfunctionalized Arenes with 1,6-Diynes via Rhodium-Catalyzed Directing-Group-Free C–H Bond Activation

Hiroto Takahashi; Yusaku Honjo; Yu Shibata; Yuki Nagashima; Ken Tanaka

doi:10.1055/a-1328-6436

Synthesis, Table of Contents

Synthesis 2021; 53(17): 3065-3074
DOI: 10.1055/a-1328-6436

special topic

Bond Activation – in Honor of Prof. Shinji Murai

Dienylation of Unfunctionalized Arenes with 1,6-Diynes via Rhodium-Catalyzed Directing-Group-Free C–H Bond Activation

Hiroto Takahashi

,

Yusaku Honjo

,

Yu Shibata

,

Yuki Nagashima

,

Ken Tanaka ∗

Abstract

All articles of this category

Abstract

It has been established that the dienylation of unfunctionalized arenes with 1,6-diynes, possessing aryl groups at the diyne termini, proceeds to give the corresponding dienylated arenes in the presence of a catalytic amount of an electron-deficient cyclopentadienyl rhodium(III) complex, [Cp^ERhCl₂]₂, and a stoichiometric amount of silver carbonate. Experimental and theoretical mechanistic studies revealed that a Cp^ERh(I) complex generated in situ might catalyze the present dienylation reaction.

Key words

alkynes - dienylation - directing group-free C–H bond activation - rhodium - unfunctionalized arenes

Full Text

References

References

For selected recent reviews, see:

1a Boyarskiy VP, Ryabukhin DS, Bokach NA, Vasilyev AV. Chem. Rev. 2016; 116: 5894
1b Yamamoto Y. Chem. Soc. Rev. 2014; 43: 1575
1c De Haro T, Nevado C. In Comprehensive Organic synthesis, 2nd ed. Knochel P. Elsevier; Amsterdam: 2014: 1621
1d Kitamura T. In Transition-Metal-Mediated Aromatic Ring Construction, Chap. 13 . Tanaka K. Wiley; Hoboken: 2013: 457
1e Kitamura T. Eur. J. Org. Chem. 2009; 1111
1f Shen HC. Tetrahedron 2008; 64: 3885
1g Nevado C, Echavarren A. Synthesis 2005; 167

2 Tanaka K, Otake Y, Wada A, Hirano M. Org. Lett. 2007; 9: 2203
3 Tsuchikama K, Kuwata Y, Tahara Y, Yoshinami Y, Shibata T. Org. Lett. 2007; 9: 3097

For the reactions of aryketones with 1,6-enynes, see:

4a Tanaka K, Otake Y, Sagae H, Noguchi K, Hirano M. Angew. Chem. Int. Ed. 2008; 47: 1312 ; see also ref. 3
4b For the reactions of aryamides and acrylamides with 1,6-diynes, see: Shibata Y, Otake Y, Hirano M, Tanaka K. Org. Lett. 2009; 11: 689

5a Aubert C, Betschmann P, Eichberg MJ, Gandon V, Heckrodt TJ, Lehmann J, Malacria M, Masjost B, Paredes E, Vollhardt KP. C, Whitener GD. Chem. Eur. J. 2007; 13: 7443
5b Aubert C, Gandon V, Geny A, Heckrodt TJ, Malacria M, Paredes E, Vollhardt KP. C. Chem. Eur. J. 2007; 13: 7466

For selected recent examples of the transition-metal-catalyzed and non-directed sp² C–H bond olefination of unfunctionalized arenes, see:

6a Ghosh K, Mihara G, Nishii Y, Miura M. Chem. Lett. 2019; 48: 148
6b Chen H, Wedi P, Meyer T, Tavakoli G, Van Gemmeren M. Angew. Chem. Int. Ed. 2018; 57: 2497
6c Wang P, Verma P, Xia G, Shi J, Qiao JX, Tao S, Cheng PT. W, Poss MA, Farmer ME, Yeung K.-S, Yu J.-Q. Nature 2017; 551: 489
6d Vora HU, Silvestri AP, Engelin CJ, Yu J.-Q. Angew. Chem. Int. Ed. 2014; 53: 2683
6e Kubota A, Emmert MH, Sanford MS. Org. Lett. 2012; 14: 1760
6f Patureau FW, Nimphius C, Glourius F. Chem. Asian J. 2012; 7: 1208

7 Shibata Y, Tanaka K. Angew. Chem. Int. Ed. 2011; 50: 10917

8a Hoshino Y, Shibata Y, Tanaka K. Adv. Synth. Catal. 2014; 356: 1577
8b Fukui M, Hoshino Y, Satoh T, Miura M, Tanaka K. Adv. Synth. Catal. 2014; 356: 1638
8c Kudo E, Shibata Y, Yamazaki M, Masutomi K, Miyauchi Y, Fukui M, Sugiyama H, Uekusa H, Satoh T, Miura M, Tanaka K. Chem. Eur. J. 2016; 22: 14190
8d Fukui M, Shibata Y, Hoshino Y, Sugiyama H, Uekusa H, Noguchi K, Tanaka K. Chem. Asian J. 2016; 11: 2260
8e Honjo Y, Shibata Y, Kudo E, Namba T, Tanaka K. Chem. Eur. J. 2018; 24: 317
8f Terasawa J, Shibata Y, Fukui M, Tanaka K. Molecules 2019; 23: 3325
8g Honjo Y, Shibata Y, Tanaka K. Chem. Eur. J. 2019; 25: 9427

For applications of 1 in C–H bond functionalizations other than annulation reactions, see:

9a Morimoto K, Itoh M, Hirano K, Satoh T, Shibata Y, Tanaka K, Miura M. Angew. Chem. Int. Ed. 2012; 51: 5359
9b Itoh M, Hirano K, Satoh T, Shibata Y, Tanaka K, Miura M. J. Org. Chem. 2013; 78: 1365
9c Baars H, Unoh Y, Okada T, Hirano K, Satoh T, Tanaka K, Bolm C, Miura M. Chem. Lett. 2014; 43: 1782
9d Takahama Y, Shibata Y, Tanaka K. Chem. Eur. J. 2015; 21: 9053
9e Shibata Y, Kudo E, Sugiyama E, Uekusa H, Tanaka K. Organometallics 2016; 35: 1547
9f Takahama Y, Shibata Y, Tanaka K. Org. Lett. 2016; 18: 2934
9g Takahama Y, Shibata Y, Tanaka K. Chem. Lett. 2016; 45: 1177
9h Yoshimura R, Shibata Y, Tanaka K. J. Org. Chem. 2019; 84: 13164

10 Unfortunately, analytically pure dienylation products could not be isolated in this reaction.

For examples of the CpRh(III) complex-catalyzed C–H bond functionalization, see:

11a Lin W, Li W, Lu D, Su F, Wen T.-B, Zhang H.-J. ACS Catal. 2018; 8: 8070
11b Yoshimura R, Tanaka K. Chem. Eur. J. 2020; 26: 4969

12 Xu S, Chen K, Chen H, Yao J, Zhu X. Chem. Eur. J. 2014; 20: 16442

The RhCl₃/i-Pr₂NEt catalyzed [2+2+2] cycloaddition of alkynes, in which RhCl₃ would be reduced by i-Pr₂NEt to afford a rhodium(I) complex, was reported, see:

13a Yoshida K, Morimoto I, Mitsudo K, Tanaka H. Tetrahedron 2008; 64: 5800
13b Yoshida K, Morimoto I, Mitsudo K, Tanaka H. Tetrahedron Lett. 2008; 49: 2363
13c Yoshida K, Morimoto I, Mitsudo K, Tanaka H. Chem. Lett. 2007; 36: 998

14 The sp² C–H bond cleavage with a cobaltacyclopentadiene is proposed in the CpCo^I-catalyzed dienylation reaction shown in Scheme 1b; see ref. 5.
15 The rhodium(I)-catalyzed [2+2+2] cycloaddition proceeded even in the presence of a stoichiometric amount of Ag₂CO₃, see: Li Y, Zhu J, Zhang L, Wu Y, Gong Y. Chem. Eur. J. 2013; 19: 8294
16 Other than 5a and 6a, an unidentified complex mixture of products was generated.
17 Lian J.-J, Chen P.-C, Lin Y.-P, Ting H.-C, Liu R.-S. J. Am. Chem. Soc. 2006; 128: 11372
18 Shibata T, Yamashita K, Katayama E, Takagi K. Tetrahedron 2002; 58: 8661
19 Bao M, Lu W, Su H, Qiu L, Xu X. Org. Biomol. Chem. 2018; 16: 3258
20 Xu T, Yang Q, Ye W, Jiang Q, Xu Z, Chen J, Yu Z. Chem. Eur. J. 2011; 17: 10547
21 Kung Y.-H, Cheng Y.-S, Tai C.-C, Liu W.-S, Shin C.-C, Ma C.-C, Tsai Y.-C, Wu T.-C, Kuo M.-Y, Wu Y.-T. Chem. Eur. J. 2010; 16: 5909
22 Aikawa H, Tago S, Umetsu K, Haginiwa N, Asao N. Tetrahedron 2009; 65: 1774
23 Hu Y.-M, Lin X.-G, Zhu T, Wan J, Sun Y.-J, Zhao Q.-S, Yu T. Synthesis 2010; 3467
24 Nguefack J, Bolitt V, Sinou D. Tetrahedron Lett. 1996; 37: 5527
25 Hsieh JC, Cheng CH. Chem. Commun. 2008; 2992
26 Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich AV, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV, Izmaylov AF, Sonnenberg JL, Williams-Young D, Ding F, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski VG, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery JA. Jr, Peralta JE, Ogliaro F, Bearpark MJ, Heyd JJ, Brothers EN, Kudin KN, Staroverov VN, Keith TA, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Millam JM, Klene M, Adamo C, Cammi R, Ochterski JW, Martin RL, Morokuma K, Farkas O, Foresman JB, Fox DJ. Gaussian 16, Revision A.03. Gaussian, Inc; Wallingford CT: 2016

27a Beche AD. Phys. Rev. A: At., Mol., Opt. Phys. 1988; 38: 3098
27b Beche AD. J. Chem. Phys. 1993; 98: 1372
27c Beche AD. J. Chem. Phys. 1993; 98: 5648
27d Lee C, Yang W, Parr RG. Phys. Rev. B: Condens. Matter Mater. Phys. 1988; 37: 785

28a Fukui K. Acc. Chem. Res. 1981; 14: 363
28b Ishida K, Morokuma K, Komornicki A. J. Chem. Phys. 1977; 66: 2153
28c Gonzalez C, Schlegel HB. J. Chem. Phys. 1989; 90: 2154
28d Schlegel HB, Gonzalez C. J. Phys. Chem. 1990; 94: 5523

Supplementary Material

Supporting Information