60916-75-8

Upstream product

• 50-00-0 formaldehyd 
• 131165-56-5 ((3aR,7aS)-2-Oxo-2,3,3a,4,5,7a-hexahydro-benzofuran-3-yl)-phosphonic acid diethyl ester 
• 131165-57-6 (3aR,7S,7aS)-3-Methylene-7-phenylselanyl-hexahydro-benzofuran-2-one 
• 54109-56-7 (3aR,7S,7aS)-7-Iodo-3-methylene-hexahydro-benzofuran-2-one 
• 131165-67-8 Cyclohex-2-enyl-(diethoxy-phosphoryl)-acetic acid 
• 1521-51-3 rac-3-bromocyclohexene 
• 131165-73-6 ((3aR,7R,7aR)-2-Oxo-7-phenylselanyl-octahydro-benzofuran-3-yl)-phosphonic acid diethyl ester 
• 131165-70-3 ((3aR,7R,7aR)-7-Iodo-2-oxo-octahydro-benzofuran-3-yl)-phosphonic acid diethyl ester 
• 130866-15-8 ethyl 2-(diethoxyphosphoryl)-2-(cyclohex-2'-enyl)acetate 
• 69637-65-6 (2-Cyclohex-2-enyl-2-methoxycarbonyl-ethyl)-trimethyl-ammonium; iodide 
• 69637-62-3 2-Cyclohex-2-enyl-3-dimethylamino-propionic acid methyl ester 
• 69637-66-7 2-(2-cyclohexenyl)-2-propenoic methylester 
• 110-83-8 cyclohexene 
• 54109-53-4 ethyl 2-(2-cyclohexenyl) acrylate 

Relevant academic research and scientific papers

Intramolecular acryloxypalladation. Stereospecific synthesis of ring fused unsaturated α-methylene γ-butyrolactones.

The intramolecular carboxypalladation reaction [Pd(OAc)2 5 mol%, NaOAc 2 eq, O2, THF, rt] of 2-(2-Cycloalken-1-yle) propenoic acids yields ring fused α-methylene γ-butyrolactones with good yields. (75-80%).

A New Synthesis of α-Methylene Lactones

Various α-diethoxyphosphoryl-γ,δ-unsaturated acids were synthesized in good yields via alkylation of ethyl (diethoxyphosphoryl)acetate with allylic bromides.Iodo- and seleno-lactonization led to α-phosphono-iodo and -seleno lactones, which underwent Wittig-Horner reaction with paraformaldehyde to produce α-methylene-γ-lactones in very good yields.This methodology was applied to a short synthesis of frullanolide.

β-Amino Ester Enolate as an Acrylate Anion Equivalent for the Synthesis of α-Methylene Esters, Acids, and Lactones

The lithium enolate (18) of methyl 3-(dimethylamino)propionate (17) has been developed as a synthetic equivalent of the α-anion (15) of acrylic acid.The enolate, obtained by treatment of the free ester (17) with lithium diisopropylamide, may be alkylated with a variety of alkyl halides to give products which may be considered to be protected acrylate esters.Unmasking is accomplished by quaternization with methyl iodide followed by DBN-induced elimination to give the free acrylates.The products derived from allylic halides may conveniently be converted into α-methylene lactones.

USE OF METHYL 3-(N,N-DIMETHYLAMINO)PROPIONATE AS A SYNTHON FOR THE CONSTRUCTION OF α-METHYLENE γ-BUTYROLACTONES

The lithium enolate of methyl 3-(N,N-dimethylamino)propionate reacts with allylic halides to give alkylation products which may be converted into α-methylene γ-butyrolactones by a reaction sequence which includes iodolactonization among other simple steps.