dc.contributor.author | Pedersen, Michael J | |
dc.contributor.author | Born, Stephen | |
dc.contributor.author | Neuenschwander, Ulrich | |
dc.contributor.author | Skovby, Tommy | |
dc.contributor.author | Mealy, Michael J | |
dc.contributor.author | Kiil, Søren | |
dc.contributor.author | Dam-Johansen, Kim | |
dc.contributor.author | Jensen, Klavs F | |
dc.date.accessioned | 2021-10-27T20:10:21Z | |
dc.date.available | 2021-10-27T20:10:21Z | |
dc.date.issued | 2018 | |
dc.identifier.uri | https://hdl.handle.net/1721.1/135019 | |
dc.description.abstract | © 2018 American Chemical Society. The kinetics of sequential addition of a distinct Grignard species onto a lactone is studied by flow chemistry. The experimental data are shown to be consistent with a kinetic model based on four reaction steps, reaction of ester to magnesium hemiacetal, rearrangement to ketone (forward and backward), and reaction of ketone to tertiary alcohol upon quenching. The experimental derived reaction mechanism is supported by ab initio molecular computations, and the predicted activation energy is in good agreement with the experimental observations. The Grignard reaction follows a substrate-independent, reductive [2 + 2] cycloaddition of the Meisenheimer/Casper type. Moreover, the rearrangement equilibrium between magnesium hemiacetal and ketone is characterized and found to be feasible. Monoaddition of the ester carbonyl group is demonstrated for fluorophenylmagnesium bromide but at reaction conditions at -40 °C with several hours of residence time. Working under cryogenic temperature conditions is essential to realizing monoaddition of the ester carbonyl group with Grignard reagents. | |
dc.language.iso | en | |
dc.publisher | American Chemical Society (ACS) | |
dc.relation.isversionof | 10.1021/ACS.IECR.8B00564 | |
dc.rights | Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. | |
dc.source | Other repository | |
dc.title | Optimization of Grignard Addition to Esters: Kinetic and Mechanistic Study of Model Phthalide Using Flow Chemistry | |
dc.type | Article | |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemical Engineering | |
dc.relation.journal | Industrial and Engineering Chemistry Research | |
dc.eprint.version | Author's final manuscript | |
dc.type.uri | http://purl.org/eprint/type/JournalArticle | |
eprint.status | http://purl.org/eprint/status/PeerReviewed | |
dc.date.updated | 2019-08-22T12:40:37Z | |
dspace.orderedauthors | Pedersen, MJ; Born, S; Neuenschwander, U; Skovby, T; Mealy, MJ; Kiil, S; Dam-Johansen, K; Jensen, KF | |
dspace.date.submission | 2019-08-22T12:40:39Z | |
mit.journal.volume | 57 | |
mit.journal.issue | 14 | |
mit.metadata.status | Authority Work and Publication Information Needed | |