Stereoselective synthesis of β-substituted α,β-unsaturated esters by dialkylcuprate coupling to the enol phosphate of β-keto esters

1979 ◽  
Vol 57 (12) ◽  
pp. 1431-1441 ◽  
Author(s):  
Fuk-Wah Sum ◽  
Larry Weiler
Keyword(s):  
Good Yield ◽  
Stereoselective Synthesis ◽  
Unsaturated Esters ◽  
Keto Esters ◽  
Tetrasubstituted Olefins ◽  
Enol Phosphate

The anions from β-keto esters or β-diketones were reacted with diethyl phosphorochloridate to yield the corresponding enol phosphates. These enol phosphates were coupled with dialkylcuprates to produce the β-substituted α,β-unsaturated esters or ketones in good yield. Starting from acyclic β-keto esters this sequence was used to stereoselectively generate tri- and tetrasubstituted olefins.

syn-Selective Reformatsky-Type Reaction of α-Silyl-α-stannylacetic Esters with Aldehydes: Stereoselective Synthesis of (E)- and (Z)-α,β-Unsaturated Esters

Synlett ◽  
1991 ◽  
Vol 1991 (12) ◽  
pp. 911-912 ◽  
Author(s):  
Shuji Akai ◽  
Yasunori Tsuzuki ◽  
Satoshi Matsuda ◽  
Shinji Kitagaki ◽  
Yasuyuki Kita
Keyword(s):  
Stereoselective Synthesis ◽  
Unsaturated Esters ◽  
Type Reaction

ChemInform Abstract: Stereoselective Synthesis of (2Z)-α-Bromo-α,β- Unsaturated Esters via Arsonium Ylide.

ChemInform ◽  
2010 ◽  
Vol 27 (24) ◽  
pp. no-no
Author(s):  
Z.-Z. HUANG ◽  
L.-L. WU ◽  
L.-S. ZHU ◽  
X. HUANG
Keyword(s):  
Stereoselective Synthesis ◽  
Unsaturated Esters

scholarly journals Palladium-catalyzed alkylation of unactivated olefins

2004 ◽  
Vol 76 (3) ◽  
pp. 671-678 ◽  
Author(s):  
Ross A. Widenhoefer
Keyword(s):  
Good Yield ◽  
Catalytic Amount ◽  
Outer Sphere ◽  
Deuterium Labeling ◽  
Carbon Nucleophiles ◽  
Keto Esters ◽  
Reactive Carbon ◽  
Aryl Ketones ◽  
Palladium Catalyzed ◽  
Hydride Elimination

The reaction of a 3-butenyl β-diketone with a catalytic amount of PdCl2(CH3CN)2 in dioxane at room temperature led to olefin hydroalkylation and formation of the corresponding 2-acylcyclohexanone in good yield as a single regioisomer. Deuterium-labeling experiments for the hydroalkylation of 7-octene-2,4-dione were in accord with a mechanism involving outer-sphere attack of the pendant enol on a palladium-complexed olefin to form a palladium cyclohexyl species, followed by palladium migration via iterative β-hydride elimination/addition and protonolysis from a palladium enolate complex. In comparison to a 3-butenyl β-diketone, reaction of a 4-pentenyl β-diketone with a catalytic amount of PdCl2(CH3CN)2 in the presence of CuCl2 led to oxidative alkylation and formation of the corresponding 2-acyl-3-methyl-2-cyclohexenone in good yield as a single isomer. Unactivated olefins tethered to less reactive carbon nucleophiles such as β-keto esters, α-aryl ketones, and even dialkyl ketones underwent palladium-catalyzed hydroalkylation in the presence of Me3SiCl or HCl to form the corresponding cyclohexanones in moderate-to-good yield with high regioselectivity.

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