Epoxide ring opening with alcohols using heterogeneous Lewis acid catalysts: Regioselectivity and mechanism

Deshpande, Nitish; Parulkar, Aamena; Joshi, Rutuja; Diep, Brian; Kulkarni, Ambarish; Brunelli, Nicholas A.

doi:10.1016/j.jcat.2018.11.038

Epoxide ring opening with alcohols using heterogeneous Lewis acid catalysts: Regioselectivity and mechanism

Journal Article · Wed Dec 19 23:00:00 EST 2018 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2018.11.038· OSTI ID:1543558

Deshpande, Nitish ^[1]; Parulkar, Aamena ^[1]; Joshi, Rutuja ^[1]; Diep, Brian ^[1]; Kulkarni, Ambarish ^[2]; ^[1]

The Ohio State Univ., Columbus, OH (United States)
Univ. of California, Davis, CA (United States)

Lewis acidic catalytic materials are investigated for the regioselective ring opening of epoxides with alcohols. For ring opening epichlorohydrin with methanol, the catalytic activity shows a strong dependence on the type of support and Lewis acidic species used. While Sn-SBA-15 is catalytically active, significantly higher catalytic activity can be achieved with hydrothermally synthesized zeolites of which Sn-Beta is 6 and 7 times more active than Zr-Beta or Hf-Beta, respectively. Sn-Beta is determined to be more active and more regioselective for epoxide ring opening of epichlorohydrin with methanol than Al-Beta. For Sn-Beta, the activation energy for the reaction between epichlorohydrin and methanol is determined to be 53 ± 7 kJ mol^-1. For epichlorohydrin, the activation energy barrier and experimentally observed regioselectivity are found using DFT to be consistent with a concerted reaction mechanism involving activation of the epoxide on an alcohol adsorbed on the catalytic site and nucleophilic attack by a second alcohol. Here, the epoxide is shown to impact the regioselectivity and the mechanism since isobutylene oxide is selectively ring opened by methanol to form the terminal alcohol. DFT calculations indicate the mechanism for isobutylene ring opening involves epoxide activation and ring opening on an alcohol adsorbed onto the catalytic site. Finally, catalyst reuse testing indicates that Sn-Beta can be used for multiple reactions with no decrease in activity and limited to no leaching of the tin site, demonstrating Sn-Beta is a promising catalytic material for epoxide ring opening reactions with alcohols.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF); Ohio State University Institute for Materials and Manufacturing Research (OSU IMR); American Chemical Society Petroleum Research Fund (ACS PRF)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1543558

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Journal Issue: C Vol. 370; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Epoxide ring opening with alcohols using heterogeneous Lewis acid catalysts: Regioselectivity and mechanism

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References (51)

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