Bruellingen, Eric, Neudoerfl, Joerg-Martin and Goldfuss, Bernd (2019). Ligand's electronegativity controls the sense of enantioselectivity in BIFOP-X palladium-catalyzed allylic alkylations. New J. Chem., 43 (39). S. 15743 - 15754. CAMBRIDGE: ROYAL SOC CHEMISTRY. ISSN 1369-9261

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Abstract

Palladium-catalyzed allylic alkylations of sodium dimethyl malonate with 1,3-diphenylallyl acetate, employing BIFOP-H (biphenylbisfencholphosphite) and analogue (i.e. BIFOP-X, X = D, Cl, CN, N-3) ligands, all yield (S)-enantiomeric products, while alkylations to cyclohexenyl acetate yield the (R)-enantiomeric C-C coupling product (up to 91% yield, 70% ee). The fluoro derivative BIFOP-F however, switches the sense of enantioselectivity, yielding the (R)-enantiomer for 1,3-diphenylallyl acetate and the (S)-enantiomer for the cyclohexenyl acetate (up to 92% yield, 67% ee). Computational analyses of transition structures (M06-2X-D3/def2-TZVP//B3LYP-D3(BJ)/def2-SVP) for these Pd-catalyzed allylic alkylations reproduce the experimental preference of BIFOP-H (and analogue BIFOP-X ligands) for (R)- or (S)-enantiomeric products of 1,3-diphenylallyl or cyclohexenyl acetate, respectively. The F-switch of the sense of enantioselectivity from BIFOP-H to BIFOP-F is also apparent computationally and is found (NBO-analyses) to originate from lp(Pd) -> sigma*(P-O) or lp(Pd) -> sigma*(P-F) hyperconjugations. The higher electronegativity of F vs. H in BIFOP-X hence controls the sense of enantioselectivity of this Pd-catalyzed allylic alkylation.

Item Type: Journal Article
Creators:
CreatorsEmailORCIDORCID Put Code
Bruellingen, EricUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Neudoerfl, Joerg-MartinUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
Goldfuss, BerndUNSPECIFIEDUNSPECIFIEDUNSPECIFIED
URN: urn:nbn:de:hbz:38-130624
DOI: 10.1039/c9nj02798j
Journal or Publication Title: New J. Chem.
Volume: 43
Number: 39
Page Range: S. 15743 - 15754
Date: 2019
Publisher: ROYAL SOC CHEMISTRY
Place of Publication: CAMBRIDGE
ISSN: 1369-9261
Language: English
Faculty: Unspecified
Divisions: Unspecified
Subjects: no entry
Uncontrolled Keywords:
KeywordsLanguage
DIALKYLZINC ADDITIONS; N-BUTYLLITHIUM; (PHOSPHANYLOXAZOLINE)PALLADIUM COMPLEXES; DENSITY FUNCTIONALS; NMR INVESTIGATIONS; FLUORINE; LITHIUM; THERMOCHEMISTRY; HYBRIDIZATION; SUBSTITUTIONMultiple languages
Chemistry, MultidisciplinaryMultiple languages
Refereed: Yes
URI: http://kups.ub.uni-koeln.de/id/eprint/13062

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