Selective Formation of Trimethylene Carbonate (TMC): Atmospheric Pressure Carbon Dioxide Utilization

Buckley, Benjamin R.; Patel, Anish P.; Wijayantha, K. G. Upul

doi:10.1002/ejoc.201403385

“…In each case good yields of the corresponding hydrocarboxylated all‐carbon quaternary center products were observed, again requiring no chromatography during isolation. Interestingly we observed a mixture of products from the reaction of 1 ac , with ring expansion also taking place to afford 2 ac′ , initially we thought this may arise through a similar ring expansion of oxetanes reported by us utilizing a magnesium sacrificial electrode and Bu 4 NI, [14] however on replacement of the Et 4 NI with LiBF 4 we still observed ring opening (although in a 1:1 ratio). We did not observe any ring expansion for the corresponding 1 ab substrate, perhaps indicating that steric hindrance around the oxetane prevents this from occurring.…”

Section: Resultssupporting

confidence: 73%

Selective Electrosynthetic Hydrocarboxylation of α,β‐Unsaturated Esters with Carbon Dioxide**

Sheta

¹

,

Alkayal

²

,

Mashaly

³

et al. 2021

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The carboxylation of low‐value commodity chemicals to provide higher‐value carboxylic acids is of significant interest. Recently alternative routes to the traditional hydroformylation processes that used potentially toxic carbon monoxide and a transition metal catalyst have appeared. A significant challenge has been the selectivity observed for olefin carboxylation. Photochemical methods have shown a viable route towards the hydrocarboxylation of α,β‐unsaturated alkenes but rely on the use of an excess reducing or amine reagent. Herein we report our investigations of an electrochemical approach that is able to hydrocarboxylate α,β‐unsaturated alkenes with excellent regioselectivity and the ability to carboxylate hindered substrates to afford α‐quaternary center carboxylic acids. The reported process requires no chromatography and the products are purified by simple crystallization from the reaction mixture after work‐up.

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“…In each case good yields of the corresponding hydrocarboxylated allcarbon quaternary center products were observed, again requiring no chromatography during isolation. Interestingly we observed am ixture of products from the reaction of 1ac, with ring expansion also taking place to afford 2ac' ',i nitially we thought this may arise through asimilar ring expansion of oxetanes reported by us utilizing am agnesium sacrificial electrode and Bu 4 NI, [14] however on replacement of the Et 4 NI with LiBF 4 we still observed ring opening (although in a1 :1 ratio). We did not observe any ring expansion for the corresponding 1ab substrate,p erhaps indicating that steric hindrance around the oxetane prevents this from occurring.…”

Section: Methodsmentioning

confidence: 52%

Selective Electrosynthetic Hydrocarboxylation of α,β‐Unsaturated Esters with Carbon Dioxide**

Sheta

¹

,

Alkayal

²

,

Mashaly

³

et al. 2021

Self Cite

View full text Add to dashboard Cite

The carboxylation of low‐value commodity chemicals to provide higher‐value carboxylic acids is of significant interest. Recently alternative routes to the traditional hydroformylation processes that used potentially toxic carbon monoxide and a transition metal catalyst have appeared. A significant challenge has been the selectivity observed for olefin carboxylation. Photochemical methods have shown a viable route towards the hydrocarboxylation of α,β‐unsaturated alkenes but rely on the use of an excess reducing or amine reagent. Herein we report our investigations of an electrochemical approach that is able to hydrocarboxylate α,β‐unsaturated alkenes with excellent regioselectivity and the ability to carboxylate hindered substrates to afford α‐quaternary center carboxylic acids. The reported process requires no chromatography and the products are purified by simple crystallization from the reaction mixture after work‐up.

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“…A more recent innovation described an electrochemically controlled oxetane/CO 2 coupling process to afford TMC under atmospheric CO 2 pressures. 17 Although metal catalysts have traditionally set benchmark activities for CO 2 -based couplings, organocatalysts are now receiving increased attention and gaining competitiveness. From an initial investigation on the preparation of fivemembered cyclic carbonates (5CCs), 18 we reported that the application of iodine (I 2 ), in combination with organic superbases provides a highly active catalytic system for PTMC synthesis.…”

Section: ■ Introductionmentioning

confidence: 99%

Selective Organocatalytic Preparation of Trimethylene Carbonate from Oxetane and Carbon Dioxide

Huang

¹

,

Jehanno

²

,

Worch

³

et al. 2020

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The organocatalytic coupling of oxetanes and carbon dioxide (CO 2 ) offers a sustainable route to poly(trimethylene carbonate)s and/or functional six-membered cyclic carbonate monomers. This transformation is more challenging than when using more strained epoxide comonomers and even more so when it is performed using metalfree routes. Herein, we report an organocatalytic oxetane/CO 2 coupling procedure that enables the selection of cyclic carbonate or polymer from a common intermediate. Using a novel I 2 -based binary catalyst system, cyclic carbonate with high selectivity (up to 94%) was obtained at 55 °C, whereas simply changing the temperature to 105 °C yielded the polycarbonate with M n of up to 6.4 kDa, thus showing that either trimethylene carbonate or its concomitant polycarbonate product can be selected solely by the manipulation of the reaction conditions.

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Selective Formation of Trimethylene Carbonate (TMC): Atmospheric Pressure Carbon Dioxide Utilization

Cited by 22 publications

References 48 publications

Selective Electrosynthetic Hydrocarboxylation of α,β‐Unsaturated Esters with Carbon Dioxide**

Selective Electrosynthetic Hydrocarboxylation of α,β‐Unsaturated Esters with Carbon Dioxide**

Selective Electrosynthetic Hydrocarboxylation of α,β‐Unsaturated Esters with Carbon Dioxide**

Selective Organocatalytic Preparation of Trimethylene Carbonate from Oxetane and Carbon Dioxide

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