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  Catalytic Asymmetric Fluorination of Copper Carbene Complexes: Preparative Advances and a Mechanistic Rationale

Buchsteiner, M., Martinez-Rodriguez, L., Jerabek, P., Pozo, I., Patzer, M., Nöthling, N., et al. (2020). Catalytic Asymmetric Fluorination of Copper Carbene Complexes: Preparative Advances and a Mechanistic Rationale. Chemistry – A European Journal, 26(11), 2509-2515. doi:10.1002/chem.202000081.

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chem202000081-s1-supporting_information_v2.pdf (Supplementary material), 15MB
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 Creators:
Buchsteiner, Michael1, Author              
Martinez-Rodriguez, Luis1, Author              
Jerabek, Paul2, Author              
Pozo, Iago1, Author              
Patzer, Michael3, Author              
Nöthling, Nils3, Author              
Lehmann, Christian W.3, Author              
Fürstner, Alois1, Author              
Affiliations:
1Research Department Fürstner, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445584              
2Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              
3Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445625              

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Free keywords: asymmetric catalysis; bisoxazoline ligands; carbene complexes; copper; organofluorine compounds
 Abstract: The Cu‐catalyzed reaction of substituted α‐diazoesters with fluoride gives α‐fluoroesters with ee values of up to 95 %, provided that chiral indane‐derived bis(oxazoline) ligands are used that carry bulky benzyl substituents at the bridge and moderately bulky isopropyl groups on their core. The apparently homogeneous solution of CsF in C6F6/hexafluoroisopropanol (HFIP) is the best reaction medium, but CsF in the biphasic mixture CH2Cl2/HFIP also provides good results. DFT studies suggest that fluoride initially attacks the Cu‐ rather than the C‐atom of the transient donor/acceptor carbene intermediate. This unusual step is followed by 1,2‐fluoride shift; for this migratory insertion to occur, the carbene must rotate about the Cu−C bond to ensure orbital overlap. The directionality of this rotatory movement within the C2‐symmetric binding site determines the sense of induction. This model is in excellent accord with the absolute configuration of the resulting product as determined by X‐ray diffraction using single crystals of this a priori wax‐like material grown by capillary crystallization.

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Language(s): eng - English
 Dates: 2020-01-072020-01-092020-02-21
 Publication Status: Published online
 Pages: 7
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/chem.202000081
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Title: Chemistry – A European Journal
  Other : Chem. – Eur. J.
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 26 (11) Sequence Number: - Start / End Page: 2509 - 2515 Identifier: ISSN: 0947-6539
CoNE: https://pure.mpg.de/cone/journals/resource/954926979058