Highly Stereoselective Gold‐Catalyzed Coupling of Diazo Reagents and Fluorinated Enol Silyl Ethers to Tetrasubstituted Alkenes

Abstract

We report a highly stereoselective synthesis of all-carbon or fluorinated tetrasubstituted alkenes from diazo reagents and fluorinated enol silyl ethers, using C-F bond as a synthetic handle. Cationic Au catalysis plays a key role in this reaction. Remarkable fluorine effects on the reactivity and selectivity was also observed.

Direct Carbohydroxylation of Arylalkenes with Allylic Alcohols: Cooperative Catalysis of Copper, Silver, and a Brønsted Acid

“…Synthetically useful functional groups,such as Cl, Br,carbonyl, and chloromethyl, remained intact during the functionalization reaction.The transition metal catalyzed functionalization of olefins is ap owerful tool to convert readily available petrochemical feedstocks into valuable synthetic building blocks. [1] The development of convenient and efficient methods for the functionalization of olefins is still ar esearch hotspot in organic synthesis although many catalytic methods for the mono-and di-functionalization of olefins have been reported over the past years.Many kind of metals,such as palladium, [2] rhodium, [3] gold, [4] nickel, [5] and copper, [6] were employed as the catalysts for this purpose.Direct carbohydroxylation of alkenes,w hich is the addition of C( alkyl and aryl) and OH to alkenes,i sa n important synthetic method for functionalization of the C=C bond. However,tothe best of our knowledge,only few papers on direct carbohydroxylation, namely arylhydroxylation of alkenes,h ave been reported, and they involve ar adical process.…”

“…The transition metal catalyzed functionalization of olefins is ap owerful tool to convert readily available petrochemical feedstocks into valuable synthetic building blocks. [1] The development of convenient and efficient methods for the functionalization of olefins is still ar esearch hotspot in organic synthesis although many catalytic methods for the mono-and di-functionalization of olefins have been reported over the past years.Many kind of metals,such as palladium, [2] rhodium, [3] gold, [4] nickel, [5] and copper, [6] were employed as the catalysts for this purpose.…”

Direct Carbohydroxylation of Arylalkenes with Allylic Alcohols: Cooperative Catalysis of Copper, Silver, and a Brønsted Acid

“…[1] The development of convenient and efficient methods for the functionalization of olefins is still ar esearch hotspot in organic synthesis although many catalytic methods for the mono-and di-functionalization of olefins have been reported over the past years.Many kind of metals,such as palladium, [2] rhodium, [3] gold, [4] nickel, [5] and copper, [6] were employed as the catalysts for this purpose.Direct carbohydroxylation of alkenes,w hich is the addition of C( alkyl and aryl) and OH to alkenes,i sa n important synthetic method for functionalization of the C=C bond. The catalytic direct carbohydroxylation of arylalkenes with allylic alcohols provided as traightforward and efficient approach for preparing 4,5-unsaturated alcohols.…”

“…[1] The development of convenient and efficient methods for the functionalization of olefins is still ar esearch hotspot in organic synthesis although many catalytic methods for the mono-and di-functionalization of olefins have been reported over the past years.Many kind of metals,such as palladium, [2] rhodium, [3] gold, [4] nickel, [5] and copper, [6] were employed as the catalysts for this purpose. [1] The development of convenient and efficient methods for the functionalization of olefins is still ar esearch hotspot in organic synthesis although many catalytic methods for the mono-and di-functionalization of olefins have been reported over the past years.Many kind of metals,such as palladium, [2] rhodium, [3] gold, [4] nickel, [5] and copper, [6] were employed as the catalysts for this purpose.…”

“…[14] Despite the importance of this type of alcohol, synthetic methodologies to access 4,5unsaturated alcohols are very limited and either suffer from low yield or do not meet the requirements of green chemistry. Thecopper catalyst was first screened in the presence of triphenylphosphine (PPh 3 ), AgSbF 6 ,a nd 4-nitrobenzoic acid BzOH) as the ligand, Lewis acid catalyst, and Brønsted acid catalyst, respectively,in1,4-dioxane containing 10 equivalents of water (H 2 O) at 100 8 8C(entries [1][2][3][4][5][6]. Thecopper catalyst was first screened in the presence of triphenylphosphine (PPh 3 ), AgSbF 6 ,a nd 4-nitrobenzoic acid BzOH) as the ligand, Lewis acid catalyst, and Brønsted acid catalyst, respectively,in1,4-dioxane containing 10 equivalents of water (H 2 O) at 100 8 8C(entries [1][2][3][4][5][6].…”