The Doyle–Kirmse reaction is an

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, mechanistic organ ...

in which a metal carbene reacts with an

allyl In organic chemistry, an allyl group is a substituent with the structural formula . It consists of a methylene bridge () attached to a vinyl group (). The name is derived from the scientific name for garlic, . In 1844, Theodor Wertheim isolated a ...

compound with transposition of the

alkene In organic chemistry, an alkene, or olefin, is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or at the terminal position. Terminal alkenes are also known as Alpha-olefin, α-olefins. The Internationa ...

and transfer of the electronegative group from the allyl onto the carbene carbon. As originally developed, an allyl

sulfide Sulfide (also sulphide in British English) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to large families o ...

reacts with

trimethylsilyldiazomethane Trimethylsilyldiazomethane is the organosilicon compound with the formula (CH3)3SiCHN2. It is classified as a diazo compound. Trimethylsilyldiazomethane is commercially available as solutions in hexanes, DCM, and ether. It is a specialized reag ...

to form the homoallyl sulfide compound. The reaction was first reported by in 1968 and modified by Michael P. Doyle in 1981. Doyle-Kirmse reaction

The Kirmse protocol required a copper salt. The

reaction mechanism In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical reaction occurs. A chemical mechanism is a theoretical conjecture that tries to describe in detail what takes place at each stage ...

involves

nucleophilic addition In organic chemistry, a nucleophilic addition (AN) reaction is an addition reaction where a chemical compound with an electrophilic double or triple bond reacts with a nucleophile, such that the double or triple bond is broken. Nucleophilic addit ...

of the

sulfur Sulfur ( American spelling and the preferred IUPAC name) or sulphur ( Commonwealth spelling) is a chemical element; it has symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms ...

to the metal carbene formed from the diazoalkane followed by a Stevens-like rearrangement. Doyle expanded the scope of the reaction to include other

diazo compound In organic chemistry, the diazo group is an organic moiety consisting of two linked nitrogen atoms at the terminal position. Overall charge-neutral organic compounds containing the diazo group bound to a carbon atom are called diazo compounds ...

s, such as

ethyl diazoacetate Ethyl diazoacetate (N=N=CHC(O)OC2H5) 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 aceta ...

, other allyl compounds, such as allyl amines and allyl halides, and use of with rhodium catalysts, such as hexadecacarbonylhexarhodium. An example is the reaction of ethyl diazoacetate with allyl iodide: Doyle diazo compound reaction

The reaction can also be catalyzed by

iron Iron is a chemical element; it has symbol Fe () and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, forming much of Earth's o ...

palladium Palladium is a chemical element; it has symbol Pd and atomic number 46. It is a rare and lustrous silvery-white metal discovered in 1802 by the English chemist William Hyde Wollaston. He named it after the asteroid Pallas (formally 2 Pallas), ...

silver Silver is a chemical element; it has Symbol (chemistry), symbol Ag () and atomic number 47. A soft, whitish-gray, lustrous transition metal, it exhibits the highest electrical conductivity, thermal conductivity, and reflectivity of any metal. ...

, and

nickel Nickel is a chemical element; it has symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive, but large pieces are slo ...

. Modifications using other carbenes are reported e.g. (2-furyl)carbenoids. The reaction is not strictly limited to allyl compounds.

Propargyl In organic chemistry, the propargyl group is a functional group of 2- propynyl with the structure . It is an alkyl group derived from propyne (). The term propargylic refers to a saturated position ( ''sp''3-hybridized) on a molecular framework ...

-sulfide substrates give

allene In organic chemistry, allenes are organic compounds in which one carbon atom has double bonds with each of its two adjacent carbon atoms (, where R is hydrogen, H or some organyl group). Allenes are classified as diene#Classes, cumulated dienes ...

products and conversely allenyl-sulfide substrates give homopropargyl products. Using metal catalysts that have

chiral Chirality () is a property of asymmetry important in several branches of science. The word ''chirality'' is derived from the Greek language, Greek (''kheir''), "hand", a familiar chiral object. An object or a system is ''chiral'' if it is dist ...

ligands leads to

stereoselectivity In chemistry, stereoselectivity is the property of a chemical reaction in which a single reactant forms an unequal mixture of stereoisomers during a non- stereospecific creation of a new stereocenter or during a non-stereospecific transformation ...

of the newly-formed carbon–carbon bond.

References

{{DEFAULTSORT:Doyle-Kirmse reaction Name reactions Pericyclic reactions Carbenes