The use of methanol as a C1 building block

Bhaskar Paul, Sabuj Kundu

Published: 2024-04-25 DOI: 10.1038/s41596-024-00978-0

Methanol

C1 building block

Transition-metal catalysis

Methylation reactions

Green chemistry

AI 解读

Extraction of nuclei from archived postmortem tissues for single-nucleus sequencing applications

High-quality and robust protein quantification in large clinical/pharmaceutical cohorts with IonStar proteomics investigation

Longitudinal interrogation of sympathetic neural circuits and hemodynamics in preclinical models

Experimental modulation of physiological force application on leg joint neurons in intactDrosophila melanogaster

Combining surface-accessible Ag and Au colloidal nanomaterials with SERS for in situ analysis of molecule–metal interactions in complex solution environments

Generation of mouse–human chimeric embryos

Labeling and tracking of immune cells in ex vivo human skin

Large-scale preparation of fluorescence multiplex host cell reactivation (FM-HCR) reporters

Mutate-and-chemical-shift-fingerprint (MCSF) to characterize excited states in RNA using NMR spectroscopy

Comprehensive multi-attribute method workflow for biotherapeutic characterization and current good manufacturing practices testing

查看全部

Sections

Figures

References

Introduction
Materials
Procedures
Troubleshooting
Timing
Anticipated results
Acknowledgements
Extended Data Fig. 1 Methanol distillation.
Extended Data Fig. 2 Ace pressure tubes.
Extended Data Fig. 3 Experimental setup for the synthesis of ligand and images of dried reagent and ligand.
Extended Data Fig. 4 Ruthenium(II) precursors.
Extended Data Fig. 5 Experimental setup for the synthesis of ruthenium (II) complexes and images of selected Ru (II) complexes.
Extended Data Fig. 6 Selected substrates and products.
Extended Data Fig. 7 Experimental setup for the synthesis of trans-RuCl(phenpyMe)(PPh3)2PF6 (Ru-3).
Extended Data Fig. 8 Experimental setup for the synthesis of NNN-OH (L2) ligand.
Extended Data Fig. 9 Ligand and cobalt precursors.
Extended Data Fig. 10 Catalytic experimental setup with different types of pressure tubes.

Natte, K., Neumann, H., Jagadeesh, R. V. & Beller, M. Convenient iron-catalyzed reductive aminations without hydrogen for selective synthesis of N-methylamines. Nat. Commun. 8, 1344 (2017).
White, T. R. et al. On-resin N-methylation of cyclic peptides for discovery of orally bioavailable scaffolds. Nat. Chem. Biol. 7, 810–817 (2011).
Chatterjee, J., Rechenmacher, F. & Kessler, H. N-Methylation of peptides and proteins: an important element for modulating biological functions. Angew. Chem. Int. Ed. 52, 254–269 (2013).
Chatterjee, J., Gilon, C., Hoffman, A. & Kessler, H. N-Methylation of peptides: a new perspective in medicinal chemistry. Acc. Chem. Res. 41, 1331–1342 (2008).
Barreiro, E. J., Kümmerle, A. E. & Fraga, C. A. M. The methylation effect in medicinal chemistry. Chem. Rev. 111, 5215–5246 (2011).
Goyal, V. et al. Recent advances in the catalytic N-methylation and N-trideuteromethylation reactions using methanol and deuterated methanol. Coord. Chem. Rev. 474, 214827 (2023).
Natte, K., Neumann, H., Beller, M. & Jagadeesh, R. V. Transition-metal-catalyzed utilization of methanol as a C1 source in organic synthesis. Angew. Chem. Int. Ed. 56, 6384–6394 (2017).
Li, Y., Cui, X., Dong, K., Junge, K. & Beller, M. Utilization of CO2 as a C1 building block for catalytic methylation reactions. ACS Catal. 7, 1077–1086 (2017).
Li, Y., Fang, X., Junge, K. & Beller, M. A general catalytic methylation of amines using carbon dioxide. Angew. Chem. Int. Ed. 52, 9568–9571 (2013).
Das, S., Bobbink, F. D., Laurenczy, G. & Dyson, P. J. Metal-free catalyst for the chemoselective methylation of amines using carbon dioxide as a carbon source. Angew. Chem. Int. Ed. 53, 12876–12879 (2014).
Das, S., Bobbink, F. D., Bulut, S., Soudani, M. & Dyson, P. J. Thiazolium carbene catalysts for the fixation of CO2 onto amines. Chem. Commun. 52, 2497–2500 (2016).
Chen, Y. Recent advances in methylation: a guide for selecting methylation reagents. Chemistry 25, 3405–3439 (2019).
Huang, C., Fu, Y., Fu, H., Jiang, Y. & Zhao, Y. Highly efficient copper-catalyzed cascade synthesis of quinazoline and quinazolinone derivatives. Chem. Commun. (Camb.) 2008, 6333–6335 (2008).
Horváth, I. T. Introduction: sustainable chemistry. Chem. Rev. 118, 369–371 (2018).
Watson, A. J. A. & Williams, J. M. J. The give and take of alcohol activation. Science 329, 635–636 (2010).
Gunanathan, C. & Milstein, D. Applications of acceptorless dehydrogenation and related transformations in chemical synthesis. Science 341, 1229712 (2013).
Moran, J., Preetz, A., Mesch, R. A. & Krische, M. J. Iridium-catalysed direct C–C coupling of methanol and allenes. Nat. Chem. 3, 287–290 (2011).
Michael, J. P. Quinoline, quinazoline and acridone alkaloids. Nat. Prod. Rep. 25, 166–187 (2008).
Rotella, D. P. Heterocycles in drug discovery: properties and preparation. In Advances in Heterocyclic Chemistry Vol. 134 (eds. Meanwell, N. A. & Lolli, M. L.) 149–183 (Academic Press, 2021).
Paul, B., Shee, S., Chakrabarti, K. & Kundu, S. Tandem transformation of nitro compounds into N-methylated amines: greener strategy for the utilization of methanol as a methylating agent. ChemSusChem 10, 2370–2374 (2017).
Paul, B., Shee, S., Panja, D., Chakrabarti, K. & Kundu, S. Direct synthesis of N,N-dimethylated and β-methyl N,N-dimethylated amines from nitriles using methanol: experimental and computational studies. ACS Catal. 8, 2890–2896 (2018).
Chakrabarti, K. et al. Utilization of MeOH as a C1 building block in tandem three-component coupling reaction. Org. Lett. 19, 4750–4753 (2017).
Paul, B., Panja, D. & Kundu, S. Ruthenium-catalyzed synthesis of N-methylated amides using methanol. Org. Lett. 21, 5843–5847 (2019).
Samim, S. A., Roy, B. C., Nayak, S. & Kundu, S. Cobalt-catalyzed tandem transformation of 2-aminobenzonitriles to quinazolinones using hydration and dehydrogenative coupling strategy. J. Org. Chem. 85, 11359–11367 (2020).
Paul, B., Chakrabarti, K. & Kundu, S. Optimum bifunctionality in a 2-(2-pyridyl-2-ol)-1,10-phenanthroline based ruthenium complex for transfer hydrogenation of ketones and nitriles: impact of the number of 2-hydroxypyridine fragments. Dalton Trans. 45, 11162–11171 (2016).
Chakrabarti, K. et al. Bifunctional Ru(ii) complex catalysed carbon–carbon bond formation: an eco-friendly hydrogen borrowing strategy. Org. Biomol. Chem. 14, 10988–10997 (2016).
Paul, B. et al. A simple and efficient in situ generated ruthenium catalyst for chemoselective transfer hydrogenation of nitroarenes: kinetic and mechanistic studies and comparison with iridium systems. RSC Adv. 6, 100532–100545 (2016).
Paul, B., Maji, M. & Kundu, S. Atom-economical and tandem conversion of nitriles to N-methylated amides using methanol and water. ACS Catal. 9, 10469–10476 (2019).
Wang, H., Huang, Y., Dai, X. & Shi, F. N-Monomethylation of amines using paraformaldehyde and H2. Chem. Commun. (Camb.) 53, 5542–5545 (2017).
Zhang, L., Zhang, Y., Deng, Y. & Shi, F. Light-promoted N,N-dimethylation of amine and nitro compound with methanol catalyzed by Pd/TiO2 at room temperature. RSC Adv. 5, 14514–14521 (2015).
Liu, J., Song, Y., Wu, X. & Ma, L. N-Dimethylation and N-functionalization of amines using Ru nanoparticle catalysts and formaldehyde or functional aldehydes as the carbon source. ACS Omega 6, 22504–22513 (2021).
Sheldon, R. A. Metrics of green chemistry and sustainability: past, present, and future. ACS Sustain. Chem. Eng. 6, 32–48 (2018).
Li, Z.-l. & Cai, C. Pd/Ni catalyzed selective N–H/C–H methylation of amides by using peroxides as the methylating reagents via a radical process. Org. Chem. Front. 4, 2207–2210 (2017).
Kumar, A., Bhatti, T. M. & Goldman, A. S. Dehydrogenation of alkanes and aliphatic groups by pincer-ligated metal complexes. Chem. Rev. 117, 12357–12384 (2017).
Haibach, M. C., Kundu, S., Brookhart, M. & Goldman, A. S. Alkane metathesis by tandem alkane-dehydrogenation–olefin-metathesis catalysis and related chemistry. Acc. Chem. Res. 45, 947–958 (2012).
Böttger, M. et al. Synthesis of new pyrrole–pyridine-based ligands using an in situ Suzuki coupling method. Beilstein J. Org. Chem. 8, 1037–1047 (2012).

The use of methanol as a C1 building block

Extended

Supplementary information

推荐阅读