Catalyst- and Additive-Free Electrochemical CO2 Fixation into Morita–Baylis–Hillman Acetates

Andrea Brunetti; Giulio Bertuzzi; Marco Bandini

doi:10.1055/a-2029-0488

Synthesis, Table of Contents

Synthesis 2023; 55(18): 3047-3055
DOI: 10.1055/a-2029-0488

paper

Special Issue Electrochemical Organic Synthesis

Catalyst- and Additive-Free Electrochemical CO₂ Fixation into Morita–Baylis–Hillman Acetates

Andrea Brunetti

^aDipartimento di Chimica ‘Giacomo Ciamician’, Alma Mater Studiorum – Università di Bologna, via Selmi 2, 40126, Bologna, Italy

,

Giulio Bertuzzi∗

^aDipartimento di Chimica ‘Giacomo Ciamician’, Alma Mater Studiorum – Università di Bologna, via Selmi 2, 40126, Bologna, Italy

^bCenter for Chemical Catalysis – C3, Alma Mater Studiorum – Università di Bologna, via Selmi 2, 40126, Bologna, Italy

,

Marco Bandini∗

^aDipartimento di Chimica ‘Giacomo Ciamician’, Alma Mater Studiorum – Università di Bologna, via Selmi 2, 40126, Bologna, Italy

^bCenter for Chemical Catalysis – C3, Alma Mater Studiorum – Università di Bologna, via Selmi 2, 40126, Bologna, Italy

› Author Affiliations

Abstract

All articles of this category

Abstract

The electrochemical carboxylation of Morita–Baylis–Hillman (MBH) acetates with CO₂ is presented. The process proceeds in the absence of transition-metal catalysts and relies on the cathodic reduction of MBH acetates to generate nucleophilic anions that are able to trap low-pressure CO₂. Valuable succinate derivatives are obtained (20 examples) in high yields (up to 90%) and with excellent functional group tolerance. A remarkable substrate-controlled (electronic nature) regioselectivity of the transformation is documented along with a mechanistic rationale based on control experiments.

Key words

electrosynthesis - carbon dioxide - MBH acetates - cathodic reduction - catalyst-free

Full Text

References

References

1a Fuchigami T, Inagi S, Atobe M. Fundamentals and Applications of Organic Electrochemistry . John Wiley & Sons; Chichester: 2020
1b Horn EJ, Rosen BR, Baran PS. ACS Cent. Sci. 2016; 2: 302
1c Yan M, Kawamata Y, Baran PS. Chem. Rev. 2017; 117: 13230
1d Wiebe A, Gieshoff T, Möhle S, Rodrigo E, Zirbes M, Waldvogel SR. Angew. Chem. Int. Ed. 2018; 57: 5594
1e Shatskiy A, Lundberg V, Kärkäs MD. ChemElectroChem 2019; 6: 4067
1f Hilt G. ChemElectroChem 2019; 7: 395
1g Kingston C, Palkowitz MD, Takahira Y, Vantourout JC, Peters BY, Kawamata Y, Baran PS. Acc. Chem. Res. 2020; 53: 72
1h Yuan Y, Lei A. Nat. Commun. 2020; 11: 802
1i Pollok D, Waldvogel SR. Chem. Sci. 2020; 11: 12386
1j Zhu C, Ang NW. G, Meyer TH, Qiu Y, Ackermann L. ACS Cent. Sci. 2021; 7: 415
1k McKenzie EC. R, Hosseini S, Couto Petro AG, Rudman KK, Gerroll BH. R, Mubarak MS, Baker LA, Little RD. Chem. Rev. 2022; 122: 3292
1l Leech MC, Lam K. Nat. Rev. Chem. 2022; 6: 275

2a Verschueren RH, De Borggraeve WM. Molecules 2019; 24: 2122
2b Liu J, Lu L, Wood D, Lin S. ACS Cent. Sci. 2020; 6: 1317
2c Rafiee M, Mayer MN, Punchihewa BT, Mumau MR. J. Org. Chem. 2021; 86: 15866
2d Liu C, Li R, Zhou W, Liang Y, Shi Y, Li R.-L, Ling Y, Yu Y, Li J, Zhang B. ACS Catal. 2021; 11: 8958
2e Davey SG. Nat. Chem. Rev. 2021; 5: 837
2f Tai NE. S, Lehnherr D, Rovis T. Chem. Rev. 2022; 122: 2487

3a Sakakura T, Choi J.-C, Yasuda Y. Chem. Rev. 2007; 107: 2365
3b Carbon Dioxide as Chemical Feedstock. Aresta M. Wiley–VCH; Weinheim: 2010
3c Aresta M, Dibenedetto A, Angelini A. Chem. Rev. 2014; 114: 1709
3d Liu Q, Wu L, Jackstell R, Beller M. Nat. Commun. 2015; 6: 5933
3e Zhang L, Hou Z. Curr. Opin. Green Sustainable Chem. 2017; 3: 17
3f Zhang Z, Ye J.-H, Wu D.-S, Zhou Y.-Q, Yu D.-G. Chem. Asian J. 2018; 13: 2292
3g Chen Y.-G, Xu X.-T, Zhang K, Li Y.-Q, Zhang L.-P, Fang P, Mei T.-S. Synthesis 2018; 50: 35
3h Cabrero-Antonino JR, Adam R, Beller M. Angew. Chem. Int. Ed. 2019; 58: 12820
3i Dabral S, Schaub T. Adv. Synth. Catal. 2019; 361: 223
3j Ran C.-K, Liao L.-L, Gao T.-Y, Gui Y.-Y, Yu D.-G. Curr. Opin. Green Sustainable Chem. 2021; 32: 100525
3k Ran C.-K, Xiao H.-Z, Liao L.-L, Ju T, Zhang W, Yu D.-G. Natl. Sci. Open 2023; 2: 20220024

4a Hong J, Li M, Zhang J, Sun B, Mo F. ChemSusChem 2019; 12: 6
4b Pimparkar S, Dalvi AK, Koodan A, Maiti S, Al-Thabaiti SA, Mokhtar M, Dutta A, Lee YR, Maiti D. Green Chem. 2021; 23: 9283
4c Ye J.-H, Ju T, Huang H, Liao L.-L, Yu D.-G. Acc. Chem. Res. 2021; 54: 2518

5a Börjesson M, Moragas T, Gallego D, Martin D. ACS Catal. 2016; 6: 6739
5b Luo J, Larrosa I. ChemSusChem 2017; 10: 3317
5c Gaydou M, Moragas T, Julià-Hernàndez F, Martin R. J. Am. Chem. Soc. 2017; 139: 12161
5d Yi Y, Hang W, Xi C. Chin. J. Org. Chem. 2021; 41: 80

For relevant examples targeting allyl electrophiles for the production of unsaturated acids, see:

5e Mita T, Higuci Y, Sato Y. Chem. Eur. J. 2015; 21: 16391
5f Chen Y.-G, Shuai B, Ma C, Zhang X.-J, Fang P, Mei T.-S. Org. Lett. 2017; 19: 2969
5g van Gemmeren M, Börjesson M, Tortajada A, Sun S.-Z, Okura K, Martin R. Angew. Chem. Int. Ed. 2017; 56: 6558
5h Liu D, Xu Z, Yu H, Fu Y. Organometallics 2021; 40: 869

For recent reviews, see:

6a Yu Z, Shi M. Chem. Commun. 2022; 58: 13539
6b Liu X.-F, Zhang K, Tao L, Lu X.-B, Zhang W.-Z. Green Chem. Eng. 2022; 3: 125

For relevant examples of electrochemical metal-catalyzed carboxylations with CO₂, see:

6c Jiao KJ, Li Z.-M, Xu X.-T, Zhang L.-P, Li Y.-Q, Zhang K, Mei TS. Org. Chem. Front. 2018; 5: 2244
6d Bazzi S, Le Duc G, Schulz E, Gosmini C, Mellah M. Org. Biomol. Chem. 2019; 17: 8546
6e Wu L.-X, Zhao Y.-G, Guan Y.-B, Wang H, Lan Y.-C, Wang H, Lu J.-X. RSC Adv. 2019; 9: 32628
6f Ang NW. J, Oliveira JC. A, Ackermann L. Angew. Chem. Int. Ed. 2020; 59: 12842
6g Sun G.-Q, Zhang W, Liao L.-L, Li L, Nie Z.-H, Wu J.-G, Zhang D, Yu D.-G. Nat. Commun. 2021; 12: 7086
6h Wu L.-X, Deng F.-J, Wu L, Wang H, Chen T, Guan Y.-B, Lu J.-X. New J. Chem. 2021; 45: 13137
6i Wang G, Chen Y, Cai P, Yi L, Li Y, Tu C, Hou Y, Wen Z, Dai L. Chem. Soc. Rev. 2021; 50: 4993
6j Wang S, Feng T, Wang Y, Qiu Y. Chem. Asian J. 2022; 17: e202200543

Selected examples of metal-free electrochemical carboxylations with CO₂. Direct carboxylation of alkyl electrophiles bearing a leaving group, see:

7a Yang D.-T, Zhu M, Schiffer ZJ, Williams K, Song X, Liu X, Manthiram K. ACS Catal. 2019; 9: 4699
7b Zhong J.-S, Yang Z.-X, Ding C.-L, Huang Y.-F, Zhao Y, Yan H, Ye K.-Y. J. Org. Chem. 2021; 86: 16162

Direct carboxylation involving the opening of three-membered rings:

7c Liao L.-L, Wang Z.-H, Cao K.-G, Sun G.-Q, Zhang W, Ran C.-K, Li Y, Chen L, Cao G.-M, Yu D.-G. J. Am. Chem. Soc. 2022; 144: 2062
7d Wang Y, Tang S, Yang G, Wang S, Ma D, Qiu Y. Angew. Chem. Int. Ed. 2022; 61: e202207746

Direct carboxylation of reactive double bonds:

7e Chen R, Tian K, He D, Gao T, Yang G, Xu J, Chen H, Wang D, Zhang Y. ACS Appl. Energy Mater. 2020; 3 5813
7f Zhang W, Lin S. J. Am. Chem. Soc. 2020; 142: 20661
7g Gao X.-T, Zhang Z, Wang X, Tian J.-S, Xie S.-L, Zhou F, Zhou J. Chem. Sci. 2020; 11: 10414
7h Alkayal A, Tabas V, Montanaro S, Wright IA, Malkov AV, Buckley BR. J. Am. Chem. Soc. 2020; 142: 1780
7i Sheta AM, Alkayal A, Mashaly MA, Said SB, Elmorsy SS, Malkov AV, Buckley BR. Angew. Chem. Int. Ed. 2021; 60: 21832
7j Zhao R, Lin Z, Maksso I, Struwe J, Ackermann L. ChemElectroChem 2022; 9: e202200989

8a Cerveri A, Pace S, Monari M, Lombardo M, Bandini M. Chem. Eur. J. 2019; 25: 15272
8b Cerveri A, Giovanelli R, Sella D, Pedrazzani R, Monari M, Nieto Faza O, Silva Lòpez C, Bandini M. Chem. Eur. J. 2021; 27: 7657
8c Lombardi L, Cerveri A, Ceccon L, Pedrazzani R, Monari M, Bertuzzi G, Bandini M. Chem. Commun. 2022; 58: 4071
8d Pintus A, Mantovani S, Kovtun A, Bertuzzi G, Melucci M, Bandini M. Chem. Eur. J. 2022; e202202440

9a Bertuzzi G, Ombrosi G, Bandini M. Org. Lett. 2022; 24: 4354
9b Rapisarda L, Fermi A, Ceroni P, Giovanelli R, Bertuzzi G, Bandini M. Chem. Commun. 2023; 59: 2664

10 For a review on reductive electrosynthetic methods, see: Claraz A, Masson G. ACS Org. Inorg. Au 2022; 2: 126
11 During the preparation of this manuscript a Pd-catalyzed electrochemical carboxylation of MBH acetates was reported, see: Tummanappalli S, Gulipalli KC, Endoori S, Bodige S, Pommidi AK, Medaboina S, Rejinthala S, Choppadandi S, Boya R, Kanuka A, Valluri M. Tetrahedron Lett. 2022; 104: 154022

For selected examples of MBH acetates as electrophilic acceptors of nucleophilic radicals, see:

12a Qi J, Zheng J, Cui S. Org. Lett. 2018; 20: 1355
12b Ye H, Ye Q, Cheng D, Li X, Xu X. Tetrahedron Lett. 2018; 59: 2046
12c Ye H, Zhao H, Ren S, Ye H, Cheng D, Li X, Xu X. Tetrahedron Lett. 2019; 60: 1302
12d Yadav AK, Sharma AK, Singh KN. Org. Chem. Front. 2019; 6: 989
12e Paria S, Carletti E, Marcon M, Cherubini-Celli A, Mazzanti A, Rancan M, Dell’Amico L, Bonchio M, Companyò X. J. Org. Chem. 2020; 85: 4463
12f Bai X, Qian L, Zhang H.-H, Yu S. Org. Lett. 2021; 23: 8322

For amine- or phosphine-catalyzed reactions featuring MBH acetates as pronucleophiles, see:

13a Liu TY, Xie M, Chen Y.-C. Chem. Soc. Rev. 2012; 41: 4101
13b Basavaiah D, Naganaboina RT. New J. Chem. 2018; 42: 14036
13c List B, Grossman O. Synfacts 2019; 15: 295
13d Calcatelli A, Cherubini-Celli A, Carletti E, Companyò X. Synthesis 2020; 52: 2922

14a Delhomme C, Weuster-Botz D, Kühn FE. Green Chem. 2009; 11: 13

For alternative preparations of 2, see for example:

14b Doulut S, Dubuc I, Rodriguez M, Vecchini F, Fulcrand H, Barelli H, Checler F, Bourdel E, Aumelas A, Lallement JC, Kitabgi P, Costentin J, Martinez J. J. Med. Chem. 1993; 36: 1369
14c Bilenko V, Jiao H, Spannenberg A, Fischer C, Reinke H, Kösters J, Komarov I, Börner A. Eur. J. Org. Chem. 2007; 5: 758

15a Koppenol WH, Rush JD. J. Phys. Chem. 1987; 91: 4429
15b Huang Y, Zhang Q, Hua L.-L, Zhan L.-W, Hou J, Li B.-D. Cell Rep. Phys. Sci. 2022; 3: 100994

For the MBH reaction of aldehydes and acrylates see the Supporting Information of:

16a Batchu H, Bhattacharyya S, Batra S. Org. Lett. 2012; 14: 6330 ; and references cited therein
16b The acetylation of the MBH adducts was carried out following the methodology reported in: Annunziata R, Benaglia M, Cinquini M, Cozzi F, Raimondi L. J. Org. Chem. 1995; 60: 4697

17 Mason PH, Emslie ND. Tetrahedron 1994; 50: 12001

Supplementary Material

Supporting Information