Organocatalytic Coupling of Bromo-Lactide with Cyclic Ethers and Carbonates to Chiral Bromo-Diesters: NHC or Anion Catalysis?

Handle URI:
http://hdl.handle.net/10754/625581
Title:
Organocatalytic Coupling of Bromo-Lactide with Cyclic Ethers and Carbonates to Chiral Bromo-Diesters: NHC or Anion Catalysis?
Authors:
Zhu, Jian-Bo; Tang, Xiaoyan; Falivene, Laura ( 0000-0003-1509-6191 ) ; Caporaso, Lucia; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Chen, Eugene Y.-X. ( 0000-0001-7512-3484 )
Abstract:
In the presence of a N-heterocyclic carbene (NHC) in THF, Br-substituted l-lactide (Br-LA) unexpectedly undergoes exclusive coupling with THF to form a chiral ω-bromo-α-keto-diester. This coupling reaction is completely selective (in a precise 1:1 fashion), readily scalable (>20 g scale), and extremely efficient (with only 50 ppm of NHC loading). Other cyclic ethers and carbonates can also undergo similar coupling with Br-LA, thus offering a class of Br-functionalized chiral diesters with various functions and chain lengths. Combined experimental and computational studies led to a coupling mechanism that proceeds through an anion (bromide)-mediated catalytic cycle, rather than an apparent NHC-catalyzed cycle.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Zhu J-B, Tang X, Falivene L, Caporaso L, Cavallo L, et al. (2017) Organocatalytic Coupling of Bromo-Lactide with Cyclic Ethers and Carbonates to Chiral Bromo-Diesters: NHC or Anion Catalysis? ACS Catalysis 7: 3929–3933. Available: http://dx.doi.org/10.1021/acscatal.7b00794.
Publisher:
American Chemical Society (ACS)
Journal:
ACS Catalysis
Issue Date:
3-May-2017
DOI:
10.1021/acscatal.7b00794
Type:
Article
ISSN:
2155-5435; 2155-5435
Sponsors:
This work was supported by the US National Science Foundation (NSF-1507702) and the W.M. Keck Foundation for the study carried out at Colorado State University, and by the funding from King Abdullah University of Science and Technology (KAUST) for the study performed at KAUST. The computing resources and the related technical support used by the University of Salerno have been provided by CRESCO/ENEAGRID High Performance Computing infrastructure and its staff.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acscatal.7b00794
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorZhu, Jian-Boen
dc.contributor.authorTang, Xiaoyanen
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCaporaso, Luciaen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorChen, Eugene Y.-X.en
dc.date.accessioned2017-10-03T12:49:27Z-
dc.date.available2017-10-03T12:49:27Z-
dc.date.issued2017-05-03en
dc.identifier.citationZhu J-B, Tang X, Falivene L, Caporaso L, Cavallo L, et al. (2017) Organocatalytic Coupling of Bromo-Lactide with Cyclic Ethers and Carbonates to Chiral Bromo-Diesters: NHC or Anion Catalysis? ACS Catalysis 7: 3929–3933. Available: http://dx.doi.org/10.1021/acscatal.7b00794.en
dc.identifier.issn2155-5435en
dc.identifier.issn2155-5435en
dc.identifier.doi10.1021/acscatal.7b00794en
dc.identifier.urihttp://hdl.handle.net/10754/625581-
dc.description.abstractIn the presence of a N-heterocyclic carbene (NHC) in THF, Br-substituted l-lactide (Br-LA) unexpectedly undergoes exclusive coupling with THF to form a chiral ω-bromo-α-keto-diester. This coupling reaction is completely selective (in a precise 1:1 fashion), readily scalable (>20 g scale), and extremely efficient (with only 50 ppm of NHC loading). Other cyclic ethers and carbonates can also undergo similar coupling with Br-LA, thus offering a class of Br-functionalized chiral diesters with various functions and chain lengths. Combined experimental and computational studies led to a coupling mechanism that proceeds through an anion (bromide)-mediated catalytic cycle, rather than an apparent NHC-catalyzed cycle.en
dc.description.sponsorshipThis work was supported by the US National Science Foundation (NSF-1507702) and the W.M. Keck Foundation for the study carried out at Colorado State University, and by the funding from King Abdullah University of Science and Technology (KAUST) for the study performed at KAUST. The computing resources and the related technical support used by the University of Salerno have been provided by CRESCO/ENEAGRID High Performance Computing infrastructure and its staff.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acscatal.7b00794en
dc.subjectbromo-lactideen
dc.subjectchiral diestersen
dc.subjectcouplingen
dc.subjectN-heterocyclic carbeneen
dc.subjectorganocatalysisen
dc.titleOrganocatalytic Coupling of Bromo-Lactide with Cyclic Ethers and Carbonates to Chiral Bromo-Diesters: NHC or Anion Catalysis?en
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalACS Catalysisen
dc.contributor.institutionDepartment of Chemistry, Colorado State University, Fort Collins, CO, 80523-1872, , United Statesen
dc.contributor.institutionDipartimento di Chimica e Biologia, Università di Salerno, Via Papa Paolo Giovanni II, Fisciano, I-84084, , Italyen
kaust.authorFalivene, Lauraen
kaust.authorCavallo, Luigien
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