Carbon–Carbon Bond Formation Mediated by an Iron(0)–Olefin Pincer Complex

Zachary S. Lincoln; Melissa R. Hoffbauer; Vlad M. Iluc

doi:10.1055/a-2615-1768

Synthesis, Table of Contents

Synthesis 2025; 57(16): 2521-2529
DOI: 10.1055/a-2615-1768

paper

Romanian Chemists in Synthesis

Carbon–Carbon Bond Formation Mediated by an Iron(0)–Olefin Pincer Complex

Authors

Zachary S. Lincoln
Melissa R. Hoffbauer
Vlad M. Iluc ∗

Abstract

All articles of this category

Abstract

C–H functionalization is a highly appealing strategy for accessing complex molecular structures. Herein, we show that π-tethered pincer ligands can engage in C–H activation when coordinated to iron. These reactions result in C(sp²)–C(sp²) bond formation through oxidative coupling and β-hydride elimination/reductive elimination pathways with alkynes and isocyanides.

Key words

low-valent iron - coupling - alkenes - alkynes - isocyanides

Full Text

References

References
1 Dalton T, Faber T, Glorius F. ACS Cent. Sci. 2021; 7: 245
2 Bergman RG. Nature 2007; 446: 391
3 Gensch T, Hopkinson MN, Glorius F, Wencel-Delord J. Chem. Soc. Rev. 2016; 45: 2900
4 Sinha SK, Ghosh P, Jain S, Maiti S, Al-Thabati SA, Alshehri AA, Mokhtar M, Maiti D. Chem. Soc. Rev. 2023; 52: 7461
5 Altus KM, Love JA. Commun. Chem. 2021; 4: 1
6 Docherty JH, Lister TM, McArthur G, Findlay MT, Domingo-Legarda P, Kenyon J, Choudhary S, Larrosa I. Chem. Rev. 2023; 123: 7692
7 Besset T, Zhao Q, Poisson T, Pannecoucke X. Synthesis 2017; 49: 4808
8 Lincoln ZS, Hoffbauer MR, Iluc VM. Inorg. Chem. Front. 2024; 11: 5579
9 Rogge T, Kaplaneris N, Chatani N, Kim J, Chang S, Punji B, Schafer LL, Musaev DG, Wencel-Delord J, Roberts CA, Sarpong R, Wilson ZE, Brimble MA, Johansson MJ, Ackermann L. Nat. Rev. Methods Primers 2021; 1: 43
10 Khusnutdinova JR, Milstein D. Angew. Chem. Int. Ed. 2015; 54: 12236
11 Elsby MR, Baker RT. Chem. Soc. Rev. 2020; 49: 8933
12 Van Der Vlugt JI. Eur. J. Inorg. Chem. 2012; 363
13 Metal-Ligand Co-operativity . van Koten G, Kirchner K, Moret M.-E. Springer; Cham: 2020
14 Vigalok A, Kraatz HB, Konstantinovsky L, Milstein D. Chem. Eur. J. 1997; 3: 253
15 Barrett BJ, Iluc VM. Inorg. Chem. 2014; 53: 7248
16 Barrett BJ, Iluc VM. Organometallics 2014; 33: 2565
17 Saes BW. H, Verhoeven DG. A, Lutz M, Klein Gebbink RJ. M, Moret M.-E. Organometallics 2015; 34: 2710
18 Polukeev AV, Wendt OF. Organometallics 2015; 34: 4262
19 Polukeev AV, Marcos R, Ahlquist MS. G, Wendt OF. Chem. Sci. 2015; 6: 2060
20 Barrett BJ, Iluc VM. Organometallics 2017; 36: 730
21 Barrett BJ, Iluc VM. Inorg. Chim. Acta 2017; 460: 35
22 Verhoeven DG. A, Negenman HA, Orsino AF, Lutz M, Moret M.-E. Inorg. Chem. 2018; 57: 10846
23 Verhoeven DG. A, Van Wiggen MA. C, Kwakernaak J, Lutz M, Klein Gebbink RJ. M, Moret ME. Chem. Eur. J. 2018; 24: 5163
24 Verhoeven DG. A, Kwakernaak J, Van Wiggen MA. C, Lutz M, Moret ME. Eur. J. Inorg. Chem. 2019; 660
25 Orsino AF, Gutiérrez Del Campo M, Lutz M, Moret M.-E. ACS Catal. 2019; 9: 2458
26 Sung S, Tinnermann H, Krämer T, Young RD. Dalton Trans. 2019; 48: 9920
27 Orsino AF, Moret M.-E. Organometallics 2020; 39: 1998
28 Verhoeven DG. A, Orsino AF, Bienenmann RL. M, Lutz M, Moret M.-E. Organometallics 2020; 39: 623
29 Sansores-Paredes ML. G, Van Der Voort S, Lutz M, Moret ME. Angew. Chem. Int. Ed. 2021; 60: 26518
30 Sansores-Paredes ML. G, Lutz M, Moret M.-E. Nat. Chem. 2024; 16: 417
31 Sansores-Paredes ML. G, Nguyen TT. T, Lutz M, Moret M.-E. Organometallics 2023; 42: 3418
32 Bauer I, Knölker H.-J. Chem. Rev. 2015; 115: 3170
33 Fürstner A. ACS Cent. Sci. 2016; 2: 778
34 Comanescu CC, Vyushkova M, Iluc VM. Chem. Sci. 2015; 6: 4570
35 Casalone G, Gavezzotti A, Mariani C, Mugnoli A, Simonetta M. Acta Crystallogr., Sect. B 1970; 26: 1
36 Lincoln ZS, Iluc VM. J. Am. Chem. Soc. 2024; 146: 17595
37 Cheng J, Chen Q, Leng X, Ye S, Deng L. Inorg. Chem. 2019; 58: 13129
38 Hoberg H, Jenni K, Angermund K, Krüger C. Angew. Chem. Int. Ed. 1987; 26: 153
39 Geier S, Goddard R, Holle S, Jolly PW, Krüger C, Lutz F. Organometallics 1997; 16: 1612
40 Casitas A, Krause H, Goddard R, Fürstner A. Angew. Chem. Int. Ed. 2015; 54: 1521
41 Casitas A, Krause H, Lutz S, Goddard R, Bill E, Fürstner A. Organometallics 2018; 37: 729
42 Burcher B, Sanders KJ, Benda L, Pintacuda G, Jeanneau E, Danopoulos AA, Braunstein P, Olivier-Bourbigou H, Breuil P.-AR. Organometallics 2017; 36: 605
43 Doyle LR, Hill PJ, Wildgoose GG, Ashley AE. Dalton Trans. 2016; 45: 7550
44 Smith JR, Sadique AR, Cundari TR, Rodgers KR, Lukat-Rodgers G, Lachicotte RJ, Flaschenriem CJ, Vela J, Holland PL. J. Am. Chem. Soc. 2006; 128: 756
45 Garhwal S, Kaushansky A, Fridman N, De Ruiter G. Chem Catal. 2021; 1: 631
46 McSkimming A, Thompson NB. Inorg. Chem. 2022; 61: 12318
47 Yu RP, Darmon JM, Hoyt JM, Margulieux GW, Turner ZR, Chirik PJ. ACS Catal. 2012; 2: 1760
48 Grubel K, Brennessel WW, Mercado BQ, Holland PL. J. Am. Chem. Soc. 2014; 136: 16807
49 Yu Y, Smith JM, Flaschenriem CJ, Holland PL. Inorg. Chem. 2006; 45: 5742
50 Kennedy CR, Zhong H, Joannou MV, Chirik PJ. Adv. Synth. Catal. 2020; 362: 404
51 Schmidt VA, Kennedy CR, Bezdek MJ, Chirik PJ. J. Am. Chem. Soc. 2018; 140: 3443
52 Hoffbauer MR, Iluc VM. J. Am. Chem. Soc. 2021; 143: 5592
53 Gao L, Wang YQ, Zhang YQ, Fu YH, Liu YY, Zhang QW. Angew. Chem. Int. Ed. 2024; 63: e202317626
54 Xiao N, Wang B, Yin J, Xu Q, Tsumori N, Sun J, Chen J. Organometallics 2004; 23: 257
55 Bauer I, Knölker H.-J. The Chemistry of Diene–Iron and Dienyl–Iron Complexes. In Patai’s Chemistry of Functional Groups . Rappoport Z. Wiley; Chichester: 2013
56 De Cian A, Weiss R. Acta Crystallogr., Sect. B 1972; 28: 3264
57 Luo J, Cui C, Xiao Z, Zhong W, Lu C, Jiang X, Li X, Liu X. Dalton Trans. 2022; 51: 11558
58 Qiu G, Ding Q, Wu J. Chem. Soc. Rev. 2013; 42: 5257
59 Collet JW, Roose TR, Ruijter E, Maes BU. W, Orru RV. A. Angew. Chem. Int. Ed. 2020; 59: 540
60 Puig J, Bonjoch J, Bradshaw B. Org. Lett. 2023; 25: 6539
61 Bellows SM, Cundari TR, Holland PL. Organometallics 2013; 32: 4741
62 Trost BM, Pinkerton AB, Toste FD, Sperrle M. J. Am. Chem. Soc. 2001; 123: 12504
63 Trost BM, Toste FD, Pinkerton AB. Chem. Rev. 2001; 101: 2067
64 Trost BM, Machacek MR, Faulk BD. J. Am. Chem. Soc. 2006; 128: 6745
65 Bellachioma G, Cardaci G, Zanazzi P. Inorg. Chem. 1987; 26: 84
66 Klose A, Solari E, Ferguson R, Floriani C, Chiesi-Villa A, Rizzoli C. Organometallics 1993; 12: 2414
67 Jiménez VG, David AH. G, Cuerva JM, Blanco V, Campaña AG. Angew. Chem. Int. Ed. 2020; 59: 15124
68 Leopold EJ. Org. Synth. 1986; 64: 164
69 Shupp JP, Rose AR, Rose MJ. Dalton Trans. 2017; 46: 9163
70 Sheldrick GM. Acta Crystallogr., Sect. C 2015; 71: 3
71 Sheldrick GM. Acta Crystallogr., Sect. A 2015; 71: 3
72 Macrae CF, Sovago I, Cottrell SJ, Galek PT. A, McCabe P, Pidcock E, Platings M, Shields GP, Stevens JS, Towler M, Wood PA. J. Appl. Crystallogr. 2020; 53: 226

Supplementary Material