Catalyst-controlled regioselective carbonylation of isobutylene oxide to pivalolactone

Aran K. Hubbell; Jessica R. Lamb; Kristine Klimovica; Michael Mulzer; Timothy D. Shaffer; Samantha N. MacMillan; Geoffrey W. Coates

doi:10.1021/acscatal.0c03492

Catalyst-controlled regioselective carbonylation of isobutylene oxide to pivalolactone

Aran K. Hubbell, Jessica R. Lamb, Kristine Klimovica, Michael Mulzer, Timothy D. Shaffer, Samantha N. MacMillan, Geoffrey W. Coates

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

Poly(pivalolactone) (PPVL) is a crystalline polyester with attractive physical and mechanical properties; however, prohibitively expensive syntheses of pivalolactone have thwarted efforts to produce PPVL on an industrial scale. Therefore, we developed a class of highly regioselective sandwich-type catalysts for the carbonylation of isobutylene oxide. These sterically encumbered complexes install carbon monoxide at the substituted epoxide carbon, generating a high level of contrasteric selectivity (up to >99:1). Further catalyst development improved catalyst solubility and reproducibility while maintaining high regioselectivity. In addition, a dibasic ester solvent extended catalyst lifetimes and suppressed side product formation. This contrasteric carbonylation of isobutylene oxide offers a route to sought-after pivalolactone and, therefore, PPVL.

Original language	English (US)
Pages (from-to)	12537-12543
Number of pages	7
Journal	ACS Catalysis
Volume	10
Issue number	21
DOIs	https://doi.org/10.1021/acscatal.0c03492
State	Published - Nov 6 2020
Externally published	Yes

Bibliographical note

Funding Information:
This research was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award No. DE-FG02-05ER15687, and ExxonMobil. J.R.L. acknowledges a graduate fellowship from the National Science Foundation (No. DGE-1144153). A.K.H. acknowledges a training grant fellowship from the National Institute of General Medical Sciences (NIGMS No. T32-GM008500). This content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institute of General Medical Sciences or the National Institutes of Health. This work made use of the NMR Facility at Cornell University, which is supported, in part, by the NSF (No. CHE-1531632), as well as the Mass Spectrometry Lab at the University of Illinois, which is supported by the NSF, Division of Biological Infrastructure (No. DBI-0100085).

Publisher Copyright:
© 2020 American Chemical Society

Keywords

Catalysis
Epoxide carbonylation
Isobutylene oxide
Pivalolactone
Poly(pivalolactone)

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title = "Catalyst-controlled regioselective carbonylation of isobutylene oxide to pivalolactone",

abstract = "Poly(pivalolactone) (PPVL) is a crystalline polyester with attractive physical and mechanical properties; however, prohibitively expensive syntheses of pivalolactone have thwarted efforts to produce PPVL on an industrial scale. Therefore, we developed a class of highly regioselective sandwich-type catalysts for the carbonylation of isobutylene oxide. These sterically encumbered complexes install carbon monoxide at the substituted epoxide carbon, generating a high level of contrasteric selectivity (up to >99:1). Further catalyst development improved catalyst solubility and reproducibility while maintaining high regioselectivity. In addition, a dibasic ester solvent extended catalyst lifetimes and suppressed side product formation. This contrasteric carbonylation of isobutylene oxide offers a route to sought-after pivalolactone and, therefore, PPVL.",

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AU - Shaffer, Timothy D.

AU - MacMillan, Samantha N.

AU - Coates, Geoffrey W.

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N2 - Poly(pivalolactone) (PPVL) is a crystalline polyester with attractive physical and mechanical properties; however, prohibitively expensive syntheses of pivalolactone have thwarted efforts to produce PPVL on an industrial scale. Therefore, we developed a class of highly regioselective sandwich-type catalysts for the carbonylation of isobutylene oxide. These sterically encumbered complexes install carbon monoxide at the substituted epoxide carbon, generating a high level of contrasteric selectivity (up to >99:1). Further catalyst development improved catalyst solubility and reproducibility while maintaining high regioselectivity. In addition, a dibasic ester solvent extended catalyst lifetimes and suppressed side product formation. This contrasteric carbonylation of isobutylene oxide offers a route to sought-after pivalolactone and, therefore, PPVL.

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Catalyst-controlled regioselective carbonylation of isobutylene oxide to pivalolactone

Abstract

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Keywords

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