Reactivity of 3, 3, 3‐Trifluoropropyne at Rhodium Complexes: Development of Hydroboration Reactions. Issue 43 (27th June 2018)

• Record Type: Journal Article
• Authors: von Hahmann, Cortney N.; Talavera, Maria; Xu, Conghui; Braun, Thomas
• Is Part Of: Chemistry. Volume 24:Issue 43(2018)
• Page Start: 11131
• Page End: 11138
• Publication Date: 2018-06-27
• Subjects: alkynes -- fluorine -- hydroboration -- ligand design -- rhodium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201801662
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The rhodium compounds [Rh(C≡CCF3 )(PEt3 )3 ] (2 ), fac ‐[RhH(C≡CCF3 )2 (PEt3 )3 ] (3 ), and fac ‐[Rh{( E )‐CH=CHCF3 }(C≡CCF3 )2 (PEt3 )3 ] (4 ) were synthesized by reactions of the rhodium(I) complexes [Rh(H)(PEt3 )3 ] (1 ) and [Rh(Bpin)(PEt3 )3 ] (5, HBpin=pinacolborane) with the alkyne 3, 3, 3‐trifluoropropyne. Reactivity studies of [Rh(C≡CCF3 )(PEt3 )3 ] (2 ) were performed with CO and 13 CO to form [Rh(C≡CCF3 )(CO)(PEt3 )3 ] (7 ) and subsequently trans ‐[Rh(C≡CCF3 )(CO)(PEt3 )2 ] (8 ) as well as the labeled derivatives. Using1–4 as catalysts, hydroboration reactions selectively afforded borylated building blocks. Abstract : [Rh]oad show : Rhodium(I) complexes react to yield new alkynyl and vinyl complexes. These complexes selectively catalyze the hydroboration reactions of 3, 3, 3‐trifluoropropyne. The catalytic studies performed herein might pave a way to access functionalized fluorinated alkynes by using borylated olefins (see scheme; HBPin=pinacolborane).