Couplage de Hiyama

The Hiyama coupling is a palladium-catalyzed cross-coupling reaction of organosilanes with organic halides used in organic chemistry to form carbon–carbon bonds (C-C bonds). This reaction was discovered in 1988 by Tamejiro Hiyama and Yasuo Hatanaka as a method to form carbon-carbon bonds synthetically with chemo- and regioselectivity. The Hiyama coupling has been applied to the synthesis of various natural products. R: aryl, alkenyl or alkynyl R': aryl, alkenyl, alkynyl or alkyl R'': Cl, F or alkyl X: Cl, Br, I or OTf The Hiyama coupling was developed to combat the issues associated with other organometallic reagents. The initial reactivity of organosilicon was not actually first reported by Hiyama, as Kumada reported a coupling reaction using organofluorosilicates shown below. Organosilanes were then discovered, by Hiyama, to have reactivity when activated by a fluoride source. This reactivity, when combined with a palladium salt, creates a carbon-carbon bond with an electrophillic carbon, like an organic halide. Compared to the inherent issues of well-used organometalics reagents, such as organomagnesium (Grignard reagents) and organocopper reagents, which are very reactive and are known to have low chemoselectivity, enough to destroy functional groups on both coupling partners, organosilicon compounds are inactive. Other organometallic reagents using metals such as zinc, tin, and boron, reduce the reactivity issue, but have other problems associated with each reagent. Organozinc reagents are moisture sensitive, organotin compounds are toxic, and organoboron reagents are not readily available, are expensive, and aren't often stable. Organosilanes are readily available compounds that, upon activation (much like organotin or organoboron compounds) from fluoride or a base, can react with organohalides to form C-C bonds in a chemo- and regioselective manner. The reaction first reported was used to couple easily made (and activated) organosilicon nucleophiles and organohalides (electrophiles) in the presence of a palladium catalyst.

Arylative Ring Expansion of 3-Vinylazetidin-3-Ols and 3-Vinyloxetan-3-Ols to Dihydrofurans by Dual Palladium and Acid Catalysis

Qian Wang, Jieping Zhu, Takuji Fujii

In contrast to the well-studied 1-vinylcyclobutanols, the reactivity of 3-vinylazetidin-3-ols 1 and 3-vinyloxetan-3-ols 2 under transition metal catalysis remains largely unexplored. We report herein their unique reactivity under dual palladium and acid ca ...

Wiley-V C H Verlag Gmbh2024

Editing Tetrasubstituted Carbon: Dual C–O Bond Functionalization of Tertiary Alcohols Enabled by Palladium-Based Dyotropic Rearrangement

Qian Wang, Jieping Zhu, Baochao Yang, Tristan Corentin Pierre Delcaillau

Many elegant asymmetric syntheses of enantioenriched tertiary alcohols have been developed, and both the transition metal-catalyzed and the radical-based peripheral functionalization of tertiary alcohols have attracted intensive research interest in recent ...

2024

Arylative Ring Expansion of 3-Vinylazetidin-3-Ols and 3-Vinyloxetan-3-Ols to Dihydrofurans by Dual Palladium and Acid Catalysis

Synergetic Support of Cartilage Homeostasis via Coupled Thermal-Hydrostatic Pressure Stimuli

Editing Tetrasubstituted Carbon: Dual C–O Bond Functionalization of Tertiary Alcohols Enabled by Palladium-Based Dyotropic Rearrangement

Editing Tetrasubstituted Carbon: Dual C–O Bond Functionalization of Tertiary Alcohols Enabled by Palladium-Based Dyotropic Rearrangement

Synergetic Support of Cartilage Homeostasis via Coupled Thermal-Hydrostatic Pressure Stimuli

Arylative Ring Expansion of 3-Vinylazetidin-3-Ols and 3-Vinyloxetan-3-Ols to Dihydrofurans by Dual Palladium and Acid Catalysis