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 ...

, hydroamination is the formal

addition Addition (usually signified by the Plus and minus signs#Plus sign, plus symbol, +) is one of the four basic Operation (mathematics), operations of arithmetic, the other three being subtraction, multiplication, and Division (mathematics), divis ...

of an bond of 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 ...

across an carbon-carbon multiple bond of 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 ...

alkyne \ce \ce Acetylene \ce \ce \ce Propyne \ce \ce \ce \ce 1-Butyne In organic chemistry, an alkyne is an unsaturated hydrocarbon containing at least one carbon—carbon triple bond. The simplest acyclic alkynes with only one triple bond and n ...

diene In organic chemistry, a diene ( ); also diolefin, ) or alkadiene) is a covalent compound that contains two double bonds, usually among carbon atoms. They thus contain two alk''ene'' units, with the standard prefix ''di'' of systematic nome ...

, or

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 ...

. In the ideal case, hydroamination is atom economical and

green Green is the color between cyan and yellow on the visible spectrum. It is evoked by light which has a dominant wavelength of roughly 495570 nm. In subtractive color systems, used in painting and color printing, it is created by a com ...

; and the products could see extensive use in fine-chemical, pharmaceutical, and agricultural industries. Hydroamination reactions occur spontaneously only for electrophilic alkenes and some dienes, but these are known by other names (e.g.

Michael addition reaction In organic chemistry, the Michael reaction or Michael 1,4 addition is a reaction between a Michael donor (an enolate or other nucleophile) and a Michael acceptor (usually an α,β-unsaturated carbonyl) to produce a Michael adduct by creating a c ...

); "hydroamination" is generally reserved for situations where the reaction requires a catalyst. Hydroamination is however of little value industrially. Hydroamination can be used intramolecularly to create heterocycles or intermolecularly with a separate amine and

unsaturated compound A saturated compound is a chemical compound (or ion) that resists addition reactions, such as hydrogenation, oxidative addition, and the binding of a Lewis base. The term is used in many contexts and classes of chemical compounds. Overall, satu ...

. File:Examples of intermolecular hydroamination.png, alt=Prototypical intermolecular hydroamination reactions., Prototypical intermolecular hydroamination reactions. File:Examples of intramolecular hydroamination (2).png, alt=Examples of intramolecular hydroamination., Examples of intramolecular hydroamination.

Formal hydroamination

The addition of hydrogen and an amino group (NR₂) using reagents other than the amine HNR₂ is known as a "formal hydroamination" reaction. Although the advantages of atom economy and/or ready available of the nitrogen source are diminished as a result, the greater thermodynamic driving force, as well as ability to tune the aminating reagent are potentially useful. In place of the amine, hydroxylamine esters and nitroarenes have been reported as nitrogen sources.

History

Hydroamination was first developed for generating fragrances from

myrcene Myrcene, or β-myrcene, is a terpene, monoterpene. A colorless oil, it occurs widely in essential oils. It is produced mainly semi-synthetically from ''Myrcia'', from which it gets its name. It is an intermediate in the production of several frag ...

. In this conversion, diethylamine adds across the diene substituent, the reaction being catalyzed by lithium diethylamide. Intramolecular hydroaminations were reported by Tobin J. Marks in 1989 using

metallocene A metallocene is a compound typically consisting of two cyclopentadienyl anions (, abbreviated Cp) bound to a metallic element, metal center (M) in the oxidation state II, with the resulting general formula Closely related to the metallocenes are ...

derived from

rare-earth metals The rare-earth elements (REE), also called the rare-earth metals or rare earths, and sometimes the lanthanides or lanthanoids (although scandium and yttrium, which do not belong to this series, are usually included as rare earths), are a set of ...

such as

lanthanum Lanthanum is a chemical element; it has symbol La and atomic number 57. It is a soft, ductile, silvery-white metal that tarnishes slowly when exposed to air. It is the eponym of the lanthanide series, a group of 15 similar elements bet ...

lutetium Lutetium is a chemical element; it has symbol Lu and atomic number 71. It is a silvery white metal, which resists corrosion in dry air, but not in moist air. Lutetium is the last element in the lanthanide series, and it is traditionally counted am ...

, and

samarium Samarium is a chemical element; it has symbol Sm and atomic number 62. It is a moderately hard silvery metal that slowly oxidizes in air. Being a typical member of the lanthanide series, samarium usually has the oxidation state +3. Compounds of s ...

. Catalytic rates correlated inversely with the

ionic radius Ionic radius, ''r''ion, is the radius of a monatomic ion in an ionic crystal structure. Although neither atoms nor ions have sharp boundaries, they are treated as if they were hard spheres with radii such that the sum of ionic radii of the cati ...

of the metal, perhaps as a consequence of

steric interference Steric effects arise from the spatial arrangement of atoms. When atoms come close together there is generally a rise in the energy of the molecule. Steric effects are nonbonding interactions that influence the shape ( conformation) and reactivi ...

from the ligands. In 1992, Marks developed the first

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 ...

hydroamination catalysts by using a chiral auxiliary, which were the first hydroamination catalysts to favor only one specific

stereoisomer In stereochemistry, stereoisomerism, or spatial isomerism, is a form of isomerism in which molecules have the same molecular formula and sequence of bonded atoms (constitution), but differ in the three-dimensional orientations of their atoms in ...

. Chiral auxiliaries on the metallocene ligands were used to dictate the stereochemistry of the product. The first non-metallocene chiral catalysts were reported in 2003, and used bisarylamido and aminophenolate ligands to give higher

enantioselectivity 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 o ...

Reaction scope

Hydroamination does not occur spontaneously, but requires catalysis. It is, however, approximately thermochemically neutral. The reaction has a large barrier, because the nitrogen atom

lone pair In chemistry, a lone pair refers to a pair of valence electrons that are not shared with another atom in a covalent bondIUPAC ''Gold Book'' definition''lone (electron) pair''/ref> and is sometimes called an unshared pair or non-bonding pair. Lone ...

and the electron rich carbon-carbon multiple bond repel each other, and hydroamination reactions, being 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, ...

, are inherently

entropically disfavoured Entropy is a scientific concept, most commonly associated with states of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics, where it was first recognized, to the microsc ...

(except in the intramolecular case). Radical amination is not a

chain reaction A chain reaction is a sequence of reactions where a reactive product or by-product causes additional reactions to take place. In a chain reaction, positive feedback leads to a self-amplifying chain of events. Chain reactions are one way that sys ...

, because hydrogen abstraction from the amine to a carbon atom is thermodynamically disfavored. Hydroamination reactions have seen extensive academic research, because they are atom-efficient processes that generally use readily available and cheap starting materials. Also, direct hydroamination strategies can in principle substantially shorten many synthesis procedures relative to classical aminations. As a result, many different situations now admit hydroamination with the appropriate catalyst. Amines that have been investigated include primary, secondary, cyclic, acyclic, and anilinic amines with diverse

steric Steric effects arise from the spatial arrangement of atoms. When atoms come close together there is generally a rise in the energy of the molecule. Steric effects are nonbonding interactions that influence the shape ( conformation) and reactivi ...

and

electronic Electronic may refer to: *Electronics, the science of how to control electric energy in semiconductors * ''Electronics'' (magazine), a defunct American trade journal *Electronic storage, the storage of data using an electronic device *Electronic c ...

substituents. Unsaturated substrates include alkenes, dienes, alkynes, and allenes. Reactions occur both intra- and intermolecularly.

Markovnikov addition In organic chemistry, Markovnikov's rule or Markownikoff's rule describes the outcome of some addition reactions. The rule was formulated by Russian chemist Vladimir Markovnikov in 1870. Explanation The rule states that with the addition of a ...

is generally favored, but some tools exist to control the regioselectivity of the addition. General_scheme_of_a_catalysed_alkyne_hydroamination

General_scheme_of_a_catalysed_alkyne_hydroamination

Catalysts

Many metal-ligand combinations have been reported to catalyze hydroamination, and can be roughly divided into three categories.

pH extremes

In the simplest case, strong Brønsted acids and bases catalyze hydroamination. One example is the ethylation of

piperidine Piperidine is an organic compound with the molecular formula (CH2)5NH. This heterocyclic amine consists of a six-membered ring containing five methylene bridges (–CH2–) and one amine bridge (–NH–). It is a colorless liquid with an odor de ...

using

ethene Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon–carbon double bonds). Ethy ...

: Such pH-extremal reactions proceed well with ethene but higher alkenes are less reactive.

Weakly-coordinating metals

Alternatively, weakly-coordinating

Lewis acids 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 sp ...

also catalyze the reaction. These include salts of the

alkali In chemistry, an alkali (; from the Arabic word , ) is a basic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a soluble base has a pH greater than 7.0. The a ...

, alkaline-earth,

rare-earth The rare-earth elements (REE), also called the rare-earth metals or rare earths, and sometimes the lanthanides or lanthanoids (although scandium and yttrium, which do not belong to this series, are usually included as rare earths), are a set of ...

, and low-valent early transition metals (e.g. titanium and zirconium), as well as

bismuth Bismuth is a chemical element; it has symbol Bi and atomic number 83. It is a post-transition metal and one of the pnictogens, with chemical properties resembling its lighter group 15 siblings arsenic and antimony. Elemental bismuth occurs nat ...

and probably certain

actinide The actinide () or actinoid () series encompasses at least the 14 metallic chemical elements in the 5f series, with atomic numbers from 89 to 102, actinium through nobelium. Number 103, lawrencium, is also generally included despite being part ...

complexes.

Zeolites Zeolites are a group of several Microporous material, microporous, crystalline aluminosilicate minerals commonly used as commercial adsorption, adsorbents and Catalysis, catalysts. They mainly consist of silicon, aluminium, oxygen, and have the ge ...

have also shown utility in hydroamination. The

mechanism Mechanism may refer to: *Mechanism (economics), a set of rules for a game designed to achieve a certain outcome **Mechanism design, the study of such mechanisms *Mechanism (engineering), rigid bodies connected by joints in order to accomplish a ...

of these hydroaminations has been well studied. First, the catalyst is activated by amide exchange, generating the active catalyst (i). Next, the alkene inserts into the Ln-N bond (ii). Finally, protonolysis occurs generating the cyclized product while also regenerating the active catalyst (iii).

Late transition-metal complexes

The complexes of late transition metals (e.g. ruthenium and palladium) and group 13 metals such as

aluminum Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...

and

indium Indium is a chemical element; it has Symbol (chemistry), symbol In and atomic number 49. It is a silvery-white post-transition metal and one of the softest elements. Chemically, indium is similar to gallium and thallium, and its properties are la ...

offer a great deal of control over the regio- and stereoselectivity of the reaction. For example, a rare and more synthetically valuable

kinetic Kinetic (Ancient Greek: κίνησις “kinesis”, movement or to move) may refer to: * Kinetic theory, describing a gas as particles in random motion * Kinetic energy, the energy of an object that it possesses due to its motion Art and ente ...

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 ...

amine product was reported when hydroaminating an

. One system utilized temperatures of 80 °C with a

rhodium Rhodium is a chemical element; it has symbol Rh and atomic number 45. It is a very rare, silvery-white, hard, corrosion-resistant transition metal. It is a noble metal and a member of the platinum group. It has only one naturally occurring isot ...

catalyst and

aniline Aniline (From , meaning ' indigo shrub', and ''-ine'' indicating a derived substance) is an organic compound with the formula . Consisting of a phenyl group () attached to an amino group (), aniline is the simplest aromatic amine. It is an in ...

derivatives as the amine. The other reported system utilized a

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), ...

catalyst at room temperature with a wide range of primary and secondary cyclic and acyclic amines. Both systems produced the desired allyl amines in high yield: In general, hydroamination with late transition-metal complexes has multiple pathways depending on the regioselective determining step. The four main categories are (1)

nucleophilic attack 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 a ...

on an alkene alkyne, or allyl ligand and (2) insertion of the alkene into the metal-amide bond. Generic catalytic cycles appear below.

Applications

No industrial applications of hydroamination are known, but hydroamination syntheses of industrial products have been performed in academia. Hydroamination has been utilized to synthesize the anti-

nausea Nausea is a diffuse sensation of unease and discomfort, sometimes perceived as an urge to vomit. It can be a debilitating symptom if prolonged and has been described as placing discomfort on the chest, abdomen, or back of the throat. Over 30 d ...

medication

cinnarizine Cinnarizine is an antihistamine and calcium channel blocker of the diphenylmethylpiperazine group. It is prescribed for nausea and vomiting due to motion sickness or other sources such as chemotherapy, vertigo, or Ménière's disease. Cinnarizin ...

in quantitative yield. Cinnarizine synthesis via hydroamination

Hydroamination is also promising for the synthesis of

alkaloid Alkaloids are a broad class of natural product, naturally occurring organic compounds that contain at least one nitrogen atom. Some synthetic compounds of similar structure may also be termed alkaloids. Alkaloids are produced by a large varie ...

s as, in the total synthesis of (-)-epimyrtine. Hydroamination in total synthesis of epimyrtine

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