RESEARCH ARTICLE Efficient Synthesis of 1,1-Dimethoxymethane from Methanol and Paraformaldehyde Catalyzed by a Molecularly defined Ni(II)- Complex Murugan Subaramanian 1 • Akash Mondal 1 • Ekambaram Balaraman 1 Received: 28 February 2019 / Revised: 1 September 2020 / Accepted: 22 October 2020 Ó The National Academy of Sciences, India 2020 Abstract A simple and highly efficient method for the preparation of 1,1-dimethoxymethane (DMM) is described using a molecularly defined NNN-Ni(II) complex (2 mol %). The reaction proceeds via the direct conden- sation reaction of methanol with paraformaldehyde under mild and neutral conditions. This atom-economical approach provides DMM in excellent yields in shorter reaction time. Graphic Abstract A simple and highly efficient method for the preparation of 1,1-dimethoxymethane (DMM) is described using a molecularly defined NNN-Ni(II) com- plex (2 mol%). The reaction proceeds via the direct con- densation reaction of methanol with paraformaldehyde under mild and neutral conditions. This highly atom-eco- nomical approach provides DMM in excellent yields in shorter reaction time. Keywords Pincer Á Nickel Á Methanol Á Homogeneous catalysis 1 Introduction Development of a new catalytic approach which can reduce the synthetic steps and toxic waste, as well as energy is becoming very important in sustainable chemical produc- tion. In recent times, transition-metal catalyzed direct functionalization of organic molecules is desirable methods in catalysis. Methanol is one of the alternative sources of fossil fuels which have been converted into value-added chemicals such as oxymethylene ethers (OMEs) and dimethyl ether (DME) by various catalytic approaches. Interestingly, 1,1 0 -dimethoxymethane (DMM) ethers are being used as a fuel additive, green solvent, as well as chemical intermediate, and have been used in perfume, cosmetic, paint, rubber and pharmaceutical industries due to their advantageous properties such as low toxicity, low boiling point and good solubility [1–3]. In particular, DMM reduces the soot formation of diesel vehicles. Moreover, DMM is widely employed as a solvent in organic synthesis owing to its stability toward a variety of reagents. Statement: Effective catalysts are critical for developing clean chemical processes in industry. Catalytic processes by transition metals are preliminarily involved in the synthesis of 80% of all industrially produced chemicals. Thus, the development and fundamental understanding of innovative new catalyst systems has clear, direct and long-term benefits to the chemical manufacturing sector and to the broader knowledge-based economy. & Ekambaram Balaraman eb.raman@iisertirupati.ac.in; balaramane2002@yahoo.com 1 Department of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati, Tirupati 517507, India 123 Proc. Natl. Acad. Sci., India, Sect. A Phys. Sci. https://doi.org/10.1007/s40010-020-00722-9