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The apparently homogeneous solution of CsF in C\n                    <jats:sub>6<\/jats:sub>\n                    F\n                    <jats:sub>6<\/jats:sub>\n                    \/hexafluoroisopropanol (HFIP) is the best reaction medium, but CsF in the biphasic mixture CH\n                    <jats:sub>2<\/jats:sub>\n                    Cl\n                    <jats:sub>2<\/jats:sub>\n                    \/HFIP also provides good results. DFT studies suggest that fluoride initially attacks the Cu\u2010 rather than the C\u2010atom of the transient donor\/acceptor carbene intermediate. This unusual step is followed by 1,2\u2010fluoride shift; for this migratory insertion to occur, the carbene must rotate about the Cu\u2212C bond to ensure orbital overlap. The directionality of this rotatory movement within the\n                    <jats:italic>C<\/jats:italic>\n                    <jats:sub>2<\/jats:sub>\n                    \u2010symmetric 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\u2010ray diffraction using single crystals of this a priori wax\u2010like material grown by capillary crystallization.\n                  <\/jats:p>","DOI":"10.1002\/chem.202000081","type":"journal-article","created":{"date-parts":[[2020,1,9]],"date-time":"2020-01-09T05:40:00Z","timestamp":1578548400000},"page":"2509-2515","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":35,"title":["Catalytic Asymmetric Fluorination of Copper Carbene Complexes: Preparative Advances and a Mechanistic Rationale"],"prefix":"10.1002","volume":"26","author":[{"given":"Michael","family":"Buchsteiner","sequence":"first","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Luis","family":"Martinez\u2010Rodriguez","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2995-9755","authenticated-orcid":false,"given":"Paul","family":"Jerabek","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr Germany"},{"name":"Present Address: Nanotechnology Department Helmholtz-Zentrum Geesthacht  21502 Geesthacht Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Iago","family":"Pozo","sequence":"additional","affiliation":[{"name":"Max-Planck-Institut f\u00fcr Kohlenforschung  45470 M\u00fclheim\/Ruhr 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