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Title: Selective Conversion of Carbon Dioxide to Formaldehyde via a Bis(silyl)acetal: Incorporation of Isotopically Labeled C1 Moieties Derived from Carbon Dioxide into Organic Molecules

Abstract

The conversion of carbon dioxide to formaldehyde is a transformation that is of considerable significance in view of the fact that formaldehyde is a widely used chemical, but this conversion is challenging because CO2 is resistant to chemical transformations. Therefore, we report here that formaldehyde can be readily obtained from CO2 at room temperature via the bis(silyl)acetal, H2C(OSiPh3)2. Specifically, formaldehyde is released from H2C(OSiPh3)2 upon treatment with CsF at room temperature. H2C(OSiPh3)2 thus serves as a formaldehyde surrogate and provides a means to incorporate CHx (x = 1 or 2) moieties into organic molecules. Here, isotopologues of H2C(OSiPh3)2 may also be synthesized, thereby providing a convenient means to use CO2 as a source of isotopic labels in organic molecules.

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Columbia University, New York, NY (United States)
Publication Date:
Research Org.:
Columbia Univ., New York, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation for a Graduate Research Fellowship
OSTI Identifier:
1656787
Grant/Contract Number:  
SC0019204; FG02-93ER14339; DGE-16-44869
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 44; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Carbon dioxide; formaldehyde; hydrosilylation; isotopologue; redox reactions; oxides; inorganic carbon compounds; organic compounds; aldehydes

Citation Formats

Rauch, Michael, Strater, Zack, and Parkin, Gerard. Selective Conversion of Carbon Dioxide to Formaldehyde via a Bis(silyl)acetal: Incorporation of Isotopically Labeled C1 Moieties Derived from Carbon Dioxide into Organic Molecules. United States: N. p., 2019. Web. doi:10.1021/jacs.9b08342.
Rauch, Michael, Strater, Zack, & Parkin, Gerard. Selective Conversion of Carbon Dioxide to Formaldehyde via a Bis(silyl)acetal: Incorporation of Isotopically Labeled C1 Moieties Derived from Carbon Dioxide into Organic Molecules. United States. https://doi.org/10.1021/jacs.9b08342
Rauch, Michael, Strater, Zack, and Parkin, Gerard. Tue . "Selective Conversion of Carbon Dioxide to Formaldehyde via a Bis(silyl)acetal: Incorporation of Isotopically Labeled C1 Moieties Derived from Carbon Dioxide into Organic Molecules". United States. https://doi.org/10.1021/jacs.9b08342. https://www.osti.gov/servlets/purl/1656787.
@article{osti_1656787,
title = {Selective Conversion of Carbon Dioxide to Formaldehyde via a Bis(silyl)acetal: Incorporation of Isotopically Labeled C1 Moieties Derived from Carbon Dioxide into Organic Molecules},
author = {Rauch, Michael and Strater, Zack and Parkin, Gerard},
abstractNote = {The conversion of carbon dioxide to formaldehyde is a transformation that is of considerable significance in view of the fact that formaldehyde is a widely used chemical, but this conversion is challenging because CO2 is resistant to chemical transformations. Therefore, we report here that formaldehyde can be readily obtained from CO2 at room temperature via the bis(silyl)acetal, H2C(OSiPh3)2. Specifically, formaldehyde is released from H2C(OSiPh3)2 upon treatment with CsF at room temperature. H2C(OSiPh3)2 thus serves as a formaldehyde surrogate and provides a means to incorporate CHx (x = 1 or 2) moieties into organic molecules. Here, isotopologues of H2C(OSiPh3)2 may also be synthesized, thereby providing a convenient means to use CO2 as a source of isotopic labels in organic molecules.},
doi = {10.1021/jacs.9b08342},
journal = {Journal of the American Chemical Society},
number = 44,
volume = 141,
place = {United States},
year = {2019},
month = {10}
}

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Scheme 1 Scheme 1: These transformations, however, require the presence of a catalyst, and although such catalysts have been known since 1981, many feature precious metals. As such, there is considerable interest in discovering catalysts that employ nonprecious metals. In this regard, we recently demonstrated that the zinc hydride compound, [Tptm]ZnH, wasmore » an effective catalyst for the hydrosilylation of CO2 by (EtO)3SiH to afford the silyl formate, HCO2Si(OEt)3, while a system comprised of [TismPriBenz]MgX (X = H, Me)13 and B(C6F5)3 was effective for selective hydrosilylation of CO2 to the bis(silyl)acetal, H2C(OSiPh3)2, as illustrated in Scheme 2.« less

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Works referencing / citing this record:

Hydroboration of carbon dioxide enabled by molecular zinc dihydrides
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