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One‐Pot Synthesis of Aldehydes or Alcohols from CO 2 via Formamides or Silyl Formates

2023; Wiley; Volume: 365; Issue: 6 Linguagem: Inglês

10.1002/adsc.202300031

1615-4169

Fan Yang, Yuta Saiki, Koichi Nakaoka, Tadashi Ema,

Organoboron and organosilicon chemistry

Advanced Synthesis & CatalysisVolume 365, Issue 6 p. 877-883 Communication One-Pot Synthesis of Aldehydes or Alcohols from CO2 via Formamides or Silyl Formates Fan Yang, Fan Yang Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Okayama, 700-8530 JapanSearch for more papers by this authorYuta Saiki, Yuta Saiki Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Okayama, 700-8530 JapanSearch for more papers by this authorKoichi Nakaoka, Koichi Nakaoka Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Okayama, 700-8530 JapanSearch for more papers by this authorTadashi Ema, Corresponding Author Tadashi Ema [email protected] (+81)86-251-8091 orcid.org/0000-0002-2160-6840 Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Okayama, 700-8530 JapanSearch for more papers by this author Fan Yang, Fan Yang Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Okayama, 700-8530 JapanSearch for more papers by this authorYuta Saiki, Yuta Saiki Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Okayama, 700-8530 JapanSearch for more papers by this authorKoichi Nakaoka, Koichi Nakaoka Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Okayama, 700-8530 JapanSearch for more papers by this authorTadashi Ema, Corresponding Author Tadashi Ema [email protected] (+81)86-251-8091 orcid.org/0000-0002-2160-6840 Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Okayama, 700-8530 JapanSearch for more papers by this author First published: 28 February 2023 https://doi.org/10.1002/adsc.202300031Citations: 1Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Graphical Abstract The solvent-free N-formylation of 2-(methylamino)pyridine with CO2 and phenylsilane was catalyzed by Cu(OAc)2 alone to give N-methyl-N-(2-pyridyl)formamide called Comins-Meyers formamide. The X-ray crystallographic analysis of a copper complex revealed a paddle-wheel structure consisting of two copper ions bridged by four acetate ions with two molecules of 2-(methylamino)pyridine on both axial sites, which suggested (i) the improved solubility of the copper ion and (ii) the enhanced nucleophilicity of the acetate ion for the activation of phenylsilane. 1H NMR spectra of benzene-d6 solutions containing Cu(OAc)2, 2-(methylamino)pyridine, and phenylsilane showed a singlet signal at 2.62 ppm, which was assigned to a catalytically active Cu−H species, and this signal disappeared upon exposure to CO2. Comins-Meyers formamide synthesized from 2-(methylamino)pyridine via the copper-catalyzed hydrosilylation of CO2 under solvent-free conditions was directly subjected to the Grignard reactions in THF for the one-pot synthesis of aldehydes or alcohols. On the other hand, silyl formates prepared from CO2 and phenylsilane using tetrabutylammonium acetate (TBAA) as an organocatalyst were also found to be good precursors of alcohols. Citing Literature Supporting Information As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Filename Description adsc202300031-sup-0001-misc_information.pdf7.6 MB Supporting Information Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article. Volume365, Issue6March 21, 2023Pages 877-883 RelatedInformation