organic chemistry Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic matter, organic materials, i.e., matter in its various forms that contain ...

, a nucleophilic addition (A_N) reaction is an

addition reaction In organic chemistry, an addition reaction is an organic reaction in which two or more molecule A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, ...

where a

chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...

with an

electrophilic In chemistry, an electrophile is a chemical species that forms bonds with nucleophiles by accepting an electron pair. Because electrophiles accept electrons, they are Lewis acids. Most electrophiles are positively charged, have an atom that carr ...

double Double, The Double or Dubble may refer to: Mathematics and computing * Multiplication by 2 * Double precision, a floating-point representation of numbers that is typically 64 bits in length * A double number of the form x+yj, where j^2=+1 * A ...

triple bond A triple bond in chemistry is a chemical bond between two atoms involving six Electron pair bond, bonding electrons instead of the usual two in a covalent bond, covalent single bond. Triple bonds are stronger than the equivalent covalent bond, sin ...

reacts with a

nucleophile In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are ...

, such that the double or triple bond is broken. Nucleophilic additions differ from

electrophilic addition In organic chemistry, an electrophilic addition (AE) reaction is an addition reaction where a chemical compound containing a double or triple bond has a π bond broken, with the formation of two new σ bonds.March, Jerry; (1985). Advanced Organic ...

s in that the former reactions involve the group to which atoms are added accepting electron pairs, whereas the latter reactions involve the group donating electron pairs.

Addition to carbon–heteroatom double bonds

Nucleophilic addition reactions of nucleophiles with electrophilic double or triple bond (π bonds) create a new carbon center with two additional single, or σ, bonds.March Jerry; (1985). Advanced Organic Chemistry reactions, mechanisms and structure (3rd ed.). New York: John Wiley & Sons, inc. Addition of a nucleophile to carbon–heteroatom double or triple bonds such as >C=O or -C≡N show great variety. These types of bonds are

polar Polar may refer to: Geography * Geographical pole, either of the two points on Earth where its axis of rotation intersects its surface ** Polar climate, the climate common in polar regions ** Polar regions of Earth, locations within the polar circ ...

(have a large difference in

electronegativity Electronegativity, symbolized as , is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the ...

between the two atoms); consequently, their carbon atoms carries a partial positive charge. This makes the molecule an electrophile, and the carbon atom the electrophilic center; this atom is the primary target for the nucleophile. Chemists have developed a geometric system to describe the approach of the nucleophile to the electrophilic center, using two angles, the Bürgi–Dunitz and the Flippin–Lodge angles after scientists that first studied and described them. : This type of reaction is also called a 1,2-nucleophilic addition. The

stereochemistry Stereochemistry, a subdiscipline of chemistry, studies the spatial arrangement of atoms that form the structure of molecules and their manipulation. The study of stereochemistry focuses on the relationships between stereoisomers, which are defined ...

of this type of nucleophilic attack is not an issue, when both alkyl substituents are dissimilar and there are not any other controlling issues such as

chelation Chelation () is a type of bonding of ions and their molecules to metal ions. It involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bonded) ligand and a single central metal atom. These l ...

with a

Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any ...

, the reaction product is a

racemate In chemistry, a racemic mixture or racemate () is a mixture that has equal amounts (50:50) of left- and right-handed enantiomers of a chiral molecule or salt. Racemic mixtures are rare in nature, but many compounds are produced industrially as r ...

. Addition reactions of this type are numerous. When the addition reaction is accompanied by an elimination the reaction is a type of substitution or an addition-elimination reaction.

Addition to carbonyl groups

With a carbonyl compound as an electrophile, the nucleophile can be: *

water Water is an inorganic compound with the chemical formula . It is a transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance. It is the main constituent of Earth's hydrosphere and the fluids of all known liv ...

hydration Hydration may refer to: * Hydrate, a substance that contains water * Hydration enthalpy, energy released through hydrating a substance * Hydration reaction, a chemical addition reaction where a hydroxyl group and proton are added to a compound * H ...

to a

geminal In chemistry, the descriptor geminal () refers to the relationship between two atoms or functional groups that are attached to the same atom. A geminal diol, for example, is a diol (a molecule that has two alcohol functional groups) attached to ...

diol A diol is a chemical compound containing two hydroxyl groups ( groups). An aliphatic diol may also be called a glycol. This pairing of functional groups is pervasive, and many subcategories have been identified. They are used as protecting gro ...

(hydrate) * an

alcohol Alcohol may refer to: Common uses * Alcohol (chemistry), a class of compounds * Ethanol, one of several alcohols, commonly known as alcohol in everyday life ** Alcohol (drug), intoxicant found in alcoholic beverages ** Alcoholic beverage, an alco ...

in acetalisation to an

acetal In organic chemistry, an acetal is a functional group with the connectivity . Here, the R groups can be organic fragments (a carbon atom, with arbitrary other atoms attached to that) or hydrogen, while the R' groups must be organic fragments n ...

* a

hydride In chemistry, a hydride is formally the anion of hydrogen (H−), a hydrogen ion with two electrons. In modern usage, this is typically only used for ionic bonds, but it is sometimes (and has been more frequently in the past) applied to all che ...

in reduction to an

* an

amine In chemistry, amines (, ) are organic compounds that contain carbon-nitrogen bonds. Amines are formed when one or more hydrogen atoms in ammonia are replaced by alkyl or aryl groups. The nitrogen atom in an amine possesses a lone pair of elec ...

with formaldehyde and a carbonyl compound in the

Mannich reaction In organic chemistry, the Mannich reaction is a three-component organic reaction that involves the amino alkylation of an acidic proton next to a carbonyl () functional group by formaldehyde () and a primary or secondary amine () or ammonia () ...

* an

enolate ion In organic chemistry, enols are a type of functional group or intermediate in organic chemistry containing a group with the formula (R = many substituents). The term ''enol'' is an abbreviation of ''alkenol'', a portmanteau deriving from "-ene ...

in an

aldol reaction The aldol reaction (aldol addition) is a Chemical reaction, reaction in organic chemistry that combines two Carbonyl group, carbonyl compounds (e.g. aldehydes or ketones) to form a new β-hydroxy carbonyl compound. Its simplest form might invol ...

Baylis–Hillman reaction In organic chemistry, the Baylis–Hillman, Morita–Baylis–Hillman, or MBH reaction is a coupling reaction, carbon–carbon bond-forming reaction between an electron-withdrawing group, activated alkene and a carbon electrophile in the presence ...

* an

organometallic Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and so ...

in the

Grignard reaction The Grignard reaction () is an organometallic chemical reaction in which, according to the classical definition, carbon alkyl, allyl, vinyl, or aryl magnesium halides (Grignard reagent) are added to the carbonyl groups of either an aldehyde or ...

or the related

Barbier reaction The Barbier reaction is an organometallic reaction between an alkyl halide (chloride, bromide, iodide), a carbonyl group and a metal. The reaction can be performed using magnesium, aluminium, zinc, indium, tin, samarium, barium or their salts. ...

or a Reformatskii reaction *

ylide An ylide () or ylid () is a neutral dipolar molecule containing a formally negatively charged atom (usually a carbanion) directly attached to a heteroatom with a formal positive charge (usually nitrogen, phosphorus or sulfur), and in which both ...

s such as a

Wittig reagent In organic chemistry, Wittig reagents are organophosphorus compounds of the formula R3P=CHR', where R is usually phenyl. They are used to convert ketones and aldehydes to alkenes: : Preparation Because they typically hydrolyze and oxidize readily, ...

or the Corey–Chaykovsky reagent or α-silyl carbanions in the Peterson olefination * a phosphonate carbanion in the

Horner–Wadsworth–Emmons reaction The Horner–Wadsworth–Emmons (HWE) reaction is a chemical reaction used in organic chemistry of stabilized phosphonate carbanions with aldehydes (or ketones) to produce predominantly E-alkenes. In 1958, Leopold Horner published a modifie ...

* a pyridine zwitterion in the Hammick reaction * an

acetylide In chemistry, an acetylide is a compound that can be viewed as the result of replacing one or both hydrogen atoms of acetylene (ethyne) by metallic or other cations. Calcium carbide is an important industrial compound, which has long been used ...

alkynylation In organic chemistry, alkynylation is an addition reaction in which a terminal alkyne () is added to a carbonyl group () to form an α-alkynyl alcohol (). When the acetylide is formed from acetylene (), the reaction gives an α-ethynyl alcohol. ...

reactions. * a cyanide ion in

cyanohydrin reaction In organic chemistry, a cyanohydrin reaction is an organic reaction in which an aldehyde () or ketone () reacts with a cyanide anion () or a nitrile () to form a cyanohydrin (). For example: \ce + \ce \longrightarrow \ce This nucleophilic ad ...

s In many nucleophilic reactions, addition to the carbonyl group is very important. In some cases, the C=O

double bond In chemistry, a double bond is a covalent bond between two atoms involving four bonding electrons as opposed to two in a single bond. Double bonds occur most commonly between two carbon atoms, for example in alkenes. Many double bonds exist betw ...

reduced Reduction, reduced, or reduce may refer to: Science and technology Chemistry * Reduction (chemistry), part of a reduction-oxidation (redox) reaction in which atoms have their oxidation state changed. ** Organic redox reaction, a redox reacti ...

to a C-O

single bond In chemistry, a single bond is a chemical bond between two atoms involving two valence electrons. That is, the atoms share one pair of electrons where the bond forms. Therefore, a single bond is a type of covalent bond. When shared, each of th ...

when the nucleophile bonds with carbon. For example, in the cyanohydrin reaction a cyanide ion forms a

C-C bond CC, cc, or C-C may refer to: Arts, entertainment, and media Fictional characters * C.C. (''Code Geass''), a character in the ''Code Geass'' anime series, pronounced "C-two" * C.C. Babcock, a character in the American sitcom ''The Nanny'' * Co ...

by breaking the carbonyl's double bond to form a

cyanohydrin In organic chemistry, a cyanohydrin or hydroxynitrile is a functional group found in organic compounds in which a cyano and a hydroxy group are attached to the same carbon atom. The general formula is , where R is H, alkyl, or aryl. Cyanohyd ...

Addition to nitriles

With

nitrile In organic chemistry, a nitrile is any organic compound that has a functional group. The name of the compound is composed of a base, which includes the carbon of the , suffixed with "nitrile", so for example is called " propionitrile" (or pr ...

electrophiles, nucleophilic addition take place by: * hydrolysis of a

to form an

amide In organic chemistry, an amide, also known as an organic amide or a carboxamide, is a chemical compound, compound with the general formula , where R, R', and R″ represent any group, typically organyl functional group, groups or hydrogen at ...

or a

carboxylic acid In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an Substituent, R-group. The general formula of a carboxylic acid is often written as or , sometimes as with R referring to an organyl ...

* organozinc nucleophiles in the

Blaise reaction The Blaise reaction is an organic reaction that forms a β-ketoester from the reaction of zinc metal with an α-bromoester and a nitrile. The reaction was first reported by Edmond Blaise (1872–1939) in 1901. The final intermediate is a metaloimi ...

s in the

Pinner reaction The Pinner reaction refers to the acid catalysed reaction of a nitrile with an alcohol to form an imino ester salt (alkyl imidate salt); this is sometimes referred to as a Pinner salt. The reaction is named after Adolf Pinner, who first described ...

. * the (same) nitrile α-carbon in the

Thorpe reaction The Thorpe reaction is a chemical reaction described as a self-condensation of aliphatic nitriles catalyzed by base to form enamines. The reaction was discovered by Jocelyn Field Thorpe. Thorpe–Ziegler reaction The Thorpe–Ziegler reaction ...

. The intramolecular version is called the Thorpe–Ziegler reaction. *

Grignard reagent Grignard reagents or Grignard compounds are chemical compounds with the general formula , where X is a halogen and R is an organic group, normally an alkyl or aryl. Two typical examples are methylmagnesium chloride and phenylmagnesium bromi ...

s to form

imine In organic chemistry, an imine ( or ) is a functional group or organic compound containing a carbon–nitrogen double bond (). The nitrogen atom can be attached to a hydrogen or an organic group (R). The carbon atom has two additional single bon ...

s. The route affords

ketone In organic chemistry, a ketone is an organic compound with the structure , where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group (a carbon-oxygen double bond C=O). The simplest ketone is acetone ( ...

s following

hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...

primary Primary or primaries may refer to: Arts, entertainment, and media Music Groups and labels * Primary (band), from Australia * Primary (musician), hip hop musician and record producer from South Korea * Primary Music, Israeli record label Work ...

s following imine reduction.

Addition to carbon–carbon double bonds

When a

X⁻ adds to an

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 ...

, the driving force is the transfer of negative charge from X to the electron-poor unsaturated -C=C- system. This occurs through the formation of a

covalent bond A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atom ...

between X and one carbon atom, concomitant with the transfer of electron density from the

pi bond In chemistry, pi bonds (π bonds) are covalent chemical bonds, in each of which two lobes of an orbital on one atom overlap with two lobes of an orbital on another atom, and in which this overlap occurs laterally. Each of these atomic orbital ...

onto the other carbon atom (step 1). During a telescoped second reaction or workup (step 2), the resulting negatively charged

carbanion In organic chemistry, a carbanion is an anion with a lone pair attached to a tervalent carbon atom. This gives the carbon atom a negative charge. Formally, a carbanion is the conjugate base of a carbon acid: : where B stands for the base (chemist ...

combines with an

Y to form the second covalent bond. : Unsubstituted and unstrained alkenes are typically insufficiently polar to admit nucleophilic addition, but a few exceptions are known. The strain energy in

fullerene A fullerene is an allotropes of carbon, allotrope of carbon whose molecules consist of carbon atoms connected by single and double bonds so as to form a closed or partially closed mesh, with fused rings of five to six atoms. The molecules may ...

s weakens their double-bonds; addition thereto is the

Bingel reaction The Bingel reaction in fullerene chemistry is a fullerene cyclopropane, cyclopropanation reaction to a methanofullerene first discovered by C. Bingel in 1993 with the bromine, bromo derivative of diethyl malonate in the presence of a base (chemist ...

. Bonds adjacent to an

electron-withdrawing An electron-withdrawing group (EWG) is a group or atom that has the ability to draw electron density toward itself and away from other adjacent atoms. This electron density transfer is often achieved by resonance or inductive effects. Electron-with ...

substituent (e.g. a

carbonyl group In organic chemistry, a carbonyl group is a functional group with the formula , composed of a carbon atom double-bonded to an oxygen atom, and it is divalent at the C atom. It is common to several classes of organic compounds (such as aldehydes ...

, or

fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...

) readily admit nucleophilic addition. In this process,

conjugate addition Nucleophilic conjugate addition is a type of organic reaction. Ordinary nucleophilic additions or 1,2-nucleophilic additions deal mostly with additions to carbonyl compounds. Simple alkene compounds do not show 1,2 reactivity due to lack of polar ...

, the nucleophile X adds β to the substituent, because then said substituent inductively stabilizes the product's negative charge.

Aromatic In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated system, conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugati ...

substituents, although typically

, can also sometimes stabilize negative charge; for example,

styrene Styrene is an organic compound with the chemical formula C6H5CH=CH2. Its structure consists of a vinyl group as substituent on benzene. Styrene is a colorless, oily liquid, although aged samples can appear yellowish. The compound evaporates easi ...

reacts in

toluene Toluene (), also known as toluol (), is a substituted aromatic hydrocarbon with the chemical formula , often abbreviated as , where Ph stands for the phenyl group. It is a colorless, water Water is an inorganic compound with the c ...

with

sodium Sodium is a chemical element; it has Symbol (chemistry), symbol Na (from Neo-Latin ) and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the peri ...

to give 1,3-diphenylpropane:''Sodium-catalyzed Side Chain Aralkylation of Alkylbenzenes with Styrene'' Herman Pines, Dieter Wunderlich J. Am. Chem. Soc.; 1958; 80(22)6001–6004.

References

{{Authority control * Reaction mechanisms