Tricyclic Sulfoxide–Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The “Matched” Diastereomer Catalyzes Asymmetric C–C Bond Formations
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2021-03-19
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ArticleAuthors
Nikol, AlexanderZhang, Ziyun
Chelouan, Ahmed
Falivene, Laura

Cavallo, Luigi

Herrera, Alberto
Heinemann, Frank W.

Escalona, Ana
Frieß, Sibylle
Grasruck, Alexander
Dorta, Romano

KAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2020-03-19Online Publication Date
2020-03-19Print Publication Date
2020-04-27Embargo End Date
2021-03-19Submitted Date
2020-02-10Permanent link to this record
http://hdl.handle.net/10754/662258
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Show full item recordAbstract
Deprotonation of phenyldibenzo[b,f]tropylidene (8) with LDA/t-BuOK followed by quenching with either diastereomer of inexpensive glucose-based t-Bu-sulfinate (R)- or (S)-11 affords a sulfoxide−alkene hybrid ligand as the diastereomeric pairs (SS,SC)-9/(SS,RC)-10 and (RS,RC)-9/ (RS,SC)-10, respectively, which via chromatographic/recrystallization may be separated into the four isomers. The optically pure diastereomeric ligands (SS,SC)-9 and (SS,RC)-10 react with [RhCl(coe)2]2 to form the dinuclear complexes (RS,SC)-11 and (RS,RC)-12, respectively, in which the bidentate ligands coordinate the metal centers through the sulfur and alkene donor functions. These complexes catalyze the conjugate addition of arylboronic acids to cyclic Michael acceptors with enantioselectivities of up to 99% ee. DFT calculations show the preponderant influence of planar chirality of the ligand alkene function. The enantioselectivity switch observed between (RS,SC)-11 and (RS,RC)-12 is explained by the inverted cis−trans coordinations of the substrate molecules in catalytic steps.Citation
Nikol, A., Zhang, Z., Chelouan, A., Falivene, L., Cavallo, L., Herrera, A., … Dorta, R. (2020). Tricyclic Sulfoxide–Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The “Matched” Diastereomer Catalyzes Asymmetric C–C Bond Formations. Organometallics. doi:10.1021/acs.organomet.0c00094Sponsors
We thank Prof. Anthony Linden (University of Zurich) for solving the crystal structure of 8 and Ms. Christina Wronna for carrying out the elemental analyses. Financial support by Friedrich–Alexander University and King Abdullah University of Science and Technology (KAUST) is acknowledged. For computer time, this research used the resources of the Supercomputing Laboratory (KSL) at KAUST.Publisher
American Chemical Society (ACS)Journal
OrganometallicsAdditional Links
https://pubs.acs.org/doi/10.1021/acs.organomet.0c00094Relations
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ae974a485f413a2113503eed53cd6c53
10.1021/acs.organomet.0c00094