Stereospecific Cross-Coupling of Secondary Organotrifluoroborates: Potassium 1‑(Benzyloxy)alkyltrifluoroborates

• Published in: Journal of the American Chemical Society Vol. 134; no. 40; pp. 16856 - 16868
• Main Authors: Molander, Gary A, Wisniewski, Steven R
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 10.10.2012; Amer Chemical Soc
• Subjects: Aldehydes - chemistry; Alkanes - chemical synthesis; Alkanes - chemistry; Benzene Derivatives - chemical synthesis; Benzene Derivatives - chemistry; Borates - chemical synthesis; Borates - chemistry; Catalysis; Chemistry; Chemistry, Multidisciplinary; Copper - chemistry; Halogenation; Palladium - chemistry; Physical Sciences; Potassium - chemistry; Science & Technology; Stereoisomerism; PALLADIUM; ALKENES; REDUCTION; RETENTION; COMPLEXES; ELIMINATION; CARBON-CARBON; ALDEHYDES; INVERSION; DIBORATION
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja307861n

Potassium 1-(alkoxy/acyloxy)alkyl­trifluoro­borates have been synthesized through a copper-catalyzed diboration of aldehydes and subsequent conversion of the resulting potassium 1-(hydroxy)alkyltrifluoroborates. The palladium-catalyzed Suzuki–Miyaura reaction employing the potassium 1-(benzyloxy)alkyltrifluoroborates with aryl and heteroaryl chlorides provides access to protected secondary alcohols in high yields. The β-hydride elimination pathway is avoided through use of the benzyl protecting group, which is proposed to stabilize the diorganopalladium intermediate by coordination of the arene to the metal center. This cross-coupling is stereospecific with complete retention of stereochemistry.