Doyle-Kirmse reaction
Encyclopedia
The Doyle-Kirmse reaction is an organic reaction
in which in the original scope an allyl
sulfide
reacts with trimethylsilyldiazomethane
to form the homoallyl sulfide compound. The reaction was first reported by W. Kirmse in 1968 and modified by M.P. Doyle in 1981.
The Kirmse protocol required a copper salt. The reaction type is nucleophilic addition
of sulfur
to a metal carbene formed from the diazoalkane followed by a Stevens-like rearrangement
.
Doyle expanded the scope of the reaction to include diazo compounds such as ethyl diazoacetate
, allyl amines and allyl halides with rhodium catalysts such as Hexadecacarbonylhexarhodium
. An example is the reaction of ethyl diazoacetate with allyl iodide:
The reaction can also be catalyzed by iron
, palladium
and silver
Modifications using other carbenes are reported e.g. (2-furyl)carbenoids. With use of certain propargyl
sulfides the reaction product is an allene
.
Organic reaction
Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic reactions, rearrangement reactions, photochemical reactions and redox reactions. In organic synthesis,...
in which in the original scope an allyl
Allyl
An allyl group is a substituent with the structural formula H2C=CH-CH2R, where R is the connection to the rest of the molecule. It is made up of a methylene , attached to a vinyl group . The name is derived from the Latin word for garlic, Allium sativum. Theodor Wertheim isolated an allyl...
sulfide
Thioether
A thioether is a functional group in organosulfur chemistry with the connectivity C-S-C as shown on right. Like many other sulfur-containing compounds, volatile thioethers have foul odors. A thioether is similar to an ether except that it contains a sulfur atom in place of the oxygen...
reacts with trimethylsilyldiazomethane
Trimethylsilyldiazomethane
Trimethylsilyldiazomethane, 3SiCHN2, is a diazo compound widely used as a less-explosive replacement for diazomethane.-Preparation:Trimethylsilyldiazomethane may be prepared from reacting methylmagnesium chloride with diphenyl phosphorazidate.-Uses:Trimethylsilyldiazomethane is a commercially...
to form the homoallyl sulfide compound. The reaction was first reported by W. Kirmse in 1968 and modified by M.P. Doyle in 1981.
The Kirmse protocol required a copper salt. The reaction type is nucleophilic addition
Nucleophilic addition
In organic chemistry, a nucleophilic addition reaction is an addition reaction where in a chemical compound a π bond is removed by the creation of two new covalent bonds by the addition of a nucleophile....
of sulfur
Sulfur
Sulfur or sulphur is the chemical element with atomic number 16. In the periodic table it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic molecules with chemical formula S8. Elemental sulfur is a bright yellow...
to a metal carbene formed from the diazoalkane followed by a Stevens-like rearrangement
Stevens rearrangement
The Stevens rearrangement in organic chemistry is an organic reaction converting quaternary ammonium salts and sulfonium salts to the corresponding amines or sulfides in presence of a strong base in a 1,2-rearrangement....
.
Doyle expanded the scope of the reaction to include diazo compounds such as ethyl diazoacetate
Ethyl diazoacetate
Ethyl diazoacetate is a diazo compound and a reagent in organic chemistry. It was discovered by Theodor Curtius in 1883. The compound can be prepared by reaction of the ethyl ester of glycine with sodium nitrite and sodium acetate in water....
, allyl amines and allyl halides with rhodium catalysts such as Hexadecacarbonylhexarhodium
Hexadecacarbonylhexarhodium
Hexadecacarbonylhexarhodium is a metal carbonyl cluster with the formula Rh616. It exists as black crystals that are soluble in organic solvents.-Discovery and synthesis:...
. An example is the reaction of ethyl diazoacetate with allyl iodide:
The reaction can also be catalyzed by iron
Iron
Iron is a chemical element with the symbol Fe and atomic number 26. It is a metal in the first transition series. It is the most common element forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust...
, palladium
Palladium
Palladium is a chemical element with the chemical symbol Pd and an atomic number of 46. It is a rare and lustrous silvery-white metal discovered in 1803 by William Hyde Wollaston. He named it after the asteroid Pallas, which was itself named after the epithet of the Greek goddess Athena, acquired...
and silver
Silver
Silver is a metallic chemical element with the chemical symbol Ag and atomic number 47. A soft, white, lustrous transition metal, it has the highest electrical conductivity of any element and the highest thermal conductivity of any metal...
Modifications using other carbenes are reported e.g. (2-furyl)carbenoids. With use of certain propargyl
Propargyl
In organic chemistry, propargyl is an alkyl functional group of 2-propynyl with the structure HC≡C−CH2−, derived from the alkyne propyne.The term propargylic refers to a saturated position on a molecular framework next to an alkynyl group...
sulfides the reaction product is an allene
Allene
An allene is a compound in which one carbon atom has double bonds with each of its two adjacent carbon centres. Allenes are classified as polyenes with cumulated dienes. The parent compound of allene is propadiene. Compounds with an allene-type structure but with more than three carbon atoms are...
.