Tricyclic Sulfoxide–Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The “Matched” Diastereomer Catalyzes Asymmetric C–C Bond Formations

Alexander Nikol; Ziyun Zhang; Ahmed Chelouan; Laura Falivene; Luigi Cavallo; Alberto Herrera; Frank W. Heinemann; Ana Escalona; Sibylle Frieß; Alexander Grasruck; Romano Dorta

doi:10.1021/acs.organomet.0c00094

Tricyclic Sulfoxide–Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The “Matched” Diastereomer Catalyzes Asymmetric C–C Bond Formations

Alexander Nikol, Ziyun Zhang, Ahmed Chelouan, Laura Falivene, Luigi Cavallo, Alberto Herrera, Frank W. Heinemann, Ana Escalona, Sibylle Frieß, Alexander Grasruck, Romano Dorta

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

1 Scopus citations

Abstract

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.

Original language	English (US)
Journal	Organometallics
DOIs	https://doi.org/10.1021/acs.organomet.0c00094
State	Published - Mar 19 2020

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10.1021/acs.organomet.0c00094

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CCDC 1965295: Experimental Crystal Structure Determination : bis(mu-chloro)-bis[5-(2-methylpropane-2-sulfinyl)-10-phenyl-5H-dibenzo[a,d][7]annulene]-di-rhodium tetrahydrofuran solvate
Nikol, A. (Creator), Zhang, Z. (Creator), Chelouan, A. (Creator), Falivene, L. (Creator), Cavallo, L. (Creator), Herrera, A. (Creator), Heinemann, F. W. (Creator), Escalona, A. (Creator), Frieß, S. (Creator), Grasruck, A. (Creator), Dorta, R. (Creator), Nikol, A. (Creator), Chelouan, A. (Creator), Herrera, A. (Creator), Heinemann, F. W. (Creator), Escalona, A. (Creator), Frieß, S. (Creator), Grasruck, A. (Creator) & Dorta, R. (Creator), Cambridge Crystallographic Data Centre, Mar 19 2020
DOI: 10.5517/ccdc.csd.cc23z1ms, http://hdl.handle.net/10754/664860
Dataset
CCDC 1965293: Experimental Crystal Structure Determination : 5-(2-methylpropane-2-sulfinyl)-10-phenyl-5H-dibenzo[a,d][7]annulene
Nikol, A. (Creator), Zhang, Z. (Creator), Chelouan, A. (Creator), Falivene, L. (Creator), Cavallo, L. (Creator), Herrera, A. (Creator), Heinemann, F. W. (Creator), Escalona, A. (Creator), Frieß, S. (Creator), Grasruck, A. (Creator), Dorta, R. (Creator), Nikol, A. (Creator), Chelouan, A. (Creator), Herrera, A. (Creator), Heinemann, F. W. (Creator), Escalona, A. (Creator), Frieß, S. (Creator), Grasruck, A. (Creator) & Dorta, R. (Creator), Cambridge Crystallographic Data Centre, Mar 19 2020
DOI: 10.5517/ccdc.csd.cc23z1kq, http://hdl.handle.net/10754/664864
Dataset
CCDC 1965296: Experimental Crystal Structure Determination : bis(mu-chloro)-bis[5-(2-methylpropane-2-sulfinyl)-10-phenyl-5H-dibenzo[a,d][7]annulene]-di-rhodium benzene solvate
Nikol, A. (Creator), Zhang, Z. (Creator), Chelouan, A. (Creator), Falivene, L. (Creator), Cavallo, L. (Creator), Herrera, A. (Creator), Heinemann, F. W. (Creator), Escalona, A. (Creator), Frieß, S. (Creator), Grasruck, A. (Creator), Dorta, R. (Creator), Nikol, A. (Creator), Chelouan, A. (Creator), Herrera, A. (Creator), Heinemann, F. W. (Creator), Escalona, A. (Creator), Frieß, S. (Creator), Grasruck, A. (Creator) & Dorta, R. (Creator), Cambridge Crystallographic Data Centre, Mar 19 2020
DOI: 10.5517/ccdc.csd.cc23z1nt, http://hdl.handle.net/10754/664859
Dataset

Cite this

Nikol, Alexander ; Zhang, Ziyun ; Chelouan, Ahmed ; Falivene, Laura ; Cavallo, Luigi ; Herrera, Alberto ; Heinemann, Frank W. ; Escalona, Ana ; Frieß, Sibylle ; Grasruck, Alexander ; Dorta, Romano. / Tricyclic Sulfoxide–Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The “Matched” Diastereomer Catalyzes Asymmetric C–C Bond Formations. In: Organometallics. 2020.

@article{a115e31617de463db6beb83e2abe8b40,

title = "Tricyclic Sulfoxide–Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The “Matched” Diastereomer Catalyzes Asymmetric C–C Bond Formations",

abstract = "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.",

author = "Alexander Nikol and Ziyun Zhang and Ahmed Chelouan and Laura Falivene and Luigi Cavallo and Alberto Herrera and Heinemann, {Frank W.} and Ana Escalona and Sibylle Frie{\ss} and Alexander Grasruck and Romano Dorta",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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.",

year = "2020",

month = mar,

day = "19",

doi = "10.1021/acs.organomet.0c00094",

language = "English (US)",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

}

Tricyclic Sulfoxide–Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The “Matched” Diastereomer Catalyzes Asymmetric C–C Bond Formations. / Nikol, Alexander; Zhang, Ziyun; Chelouan, Ahmed; Falivene, Laura; Cavallo, Luigi; Herrera, Alberto; Heinemann, Frank W.; Escalona, Ana; Frieß, Sibylle; Grasruck, Alexander; Dorta, Romano.

In: Organometallics, 19.03.2020.

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

TY - JOUR

T1 - Tricyclic Sulfoxide–Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The “Matched” Diastereomer Catalyzes Asymmetric C–C Bond Formations

AU - Nikol, Alexander

AU - Zhang, Ziyun

AU - Chelouan, Ahmed

AU - Falivene, Laura

AU - Cavallo, Luigi

AU - Herrera, Alberto

AU - Heinemann, Frank W.

AU - Escalona, Ana

AU - Frieß, Sibylle

AU - Grasruck, Alexander

AU - Dorta, Romano

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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.

PY - 2020/3/19

Y1 - 2020/3/19

N2 - 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.

AB - 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.

UR - http://hdl.handle.net/10754/662258

UR - https://pubs.acs.org/doi/10.1021/acs.organomet.0c00094

UR - http://www.scopus.com/inward/record.url?scp=85082312662&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.0c00094

DO - 10.1021/acs.organomet.0c00094

M3 - Article

JO - Organometallics

JF - Organometallics

SN - 0276-7333

ER -

Tricyclic Sulfoxide–Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The “Matched” Diastereomer Catalyzes Asymmetric C–C Bond Formations

Abstract

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CCDC 1965295: Experimental Crystal Structure Determination : bis(mu-chloro)-bis[5-(2-methylpropane-2-sulfinyl)-10-phenyl-5H-dibenzo[a,d][7]annulene]-di-rhodium tetrahydrofuran solvate

CCDC 1965293: Experimental Crystal Structure Determination : 5-(2-methylpropane-2-sulfinyl)-10-phenyl-5H-dibenzo[a,d][7]annulene

CCDC 1965296: Experimental Crystal Structure Determination : bis(mu-chloro)-bis[5-(2-methylpropane-2-sulfinyl)-10-phenyl-5H-dibenzo[a,d][7]annulene]-di-rhodium benzene solvate

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