A Caltech Library Service

Investigations of an Unexpected [2+2] Photocycloaddition in the Synthesis of (−)-Scabrolide A from Quantum Mechanics Calculations

Zhang, Tianyi and Cusumano, Alexander Q. and Hafeman, Nicholas J. and Loskot, Steven A. and Reimann, Christopher E. and Virgil, Scott C. and Goddard, William A. and Stoltz, Brian M. (2022) Investigations of an Unexpected [2+2] Photocycloaddition in the Synthesis of (−)-Scabrolide A from Quantum Mechanics Calculations. Journal of Organic Chemistry, 87 (21). pp. 14115-14124. ISSN 0022-3263. doi:10.1021/acs.joc.2c01693.

Full text is not posted in this repository. Consult Related URLs below.

Use this Persistent URL to link to this item:


It is imperative to develop efficient CO₂ capture and activation technologies to combat the rising levels of deleterious greenhouse gases in the atmosphere. Using Quantum Mechanics methods (Density Functional Theory), we propose and evaluate several metal-free and metal-containing phosphines that provide strong CO₂ binding under ambient conditions. Depending on the electron donating capacity of the phosphine and the ability of the P-bound ligands to hydrogen bond to the CO₂, we find that the CO₂ binding can be as strong as −18.6 kcal/mol downhill, which should be quite adequate for ambient conditions. We explore some modifications of the phosphine to improve CO₂ binding, and we elucidate which chemical descriptors correlate directly with CO₂ binding energy. Specifically, we find that charge accumulation on the CO₂ unit of the CO₂-bound adduct has the greatest correlation with CO₂ binding affinity. Finally, we probe the mechanism for CO₂ reduction to CO and methanol in aqueous media.

Item Type:Article
Related URLs:
URLURL TypeDescription
Zhang, Tianyi0000-0001-8289-3102
Cusumano, Alexander Q.0000-0002-2914-2008
Hafeman, Nicholas J.0000-0001-7525-7597
Reimann, Christopher E.0000-0003-3274-7590
Virgil, Scott C.0000-0001-8586-5641
Goddard, William A.0000-0003-0097-5716
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:The authors wish to thank the NSF (CHE-1800511) and the California Institute of Technology for funding. WAG thanks Hong Kong Quantum AI lab Ltd. in the form of the InnoHK initiative for support.
Funding AgencyGrant Number
Hong Kong Quantum AI Lab Ltd.UNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Issue or Number:21
Record Number:CaltechAUTHORS:20221216-550232000.1
Persistent URL:
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:118391
Deposited By: Research Services Depository
Deposited On:17 Dec 2022 03:42
Last Modified:17 Dec 2022 03:42

Repository Staff Only: item control page