A superbase is a compound that has a particularly high affinity for protons. Superbases are of theoretical interest and potentially valuable in organic synthesis. [1] [2] Superbases have been described and used since the 1850s. [3] [4]
A superbase is a compound that has a particularly high affinity for protons. Superbases are of theoretical interest and potentially valuable in organic synthesis. [1] [2] Superbases have been described and used since the 1850s. [3] [4]
Generically IUPAC defines a superbase as a "compound having a very high basicity, such as lithium diisopropylamide." [5] Superbases are often defined in two broad categories, organic and organometallic.
Organic superbases are charge-neutral compounds with basicities greater than that of proton sponge (pKBH+ = 18.6 in MeCN)." [1] In a related definition: any species with a higher absolute proton affinity (APA = 245.3 kcal/mol) and intrinsic gas phase basicity (GB = 239 kcal/mol) than proton sponge. [6] Common superbases of this variety feature amidine, guanidine, and phosphazene functional groups. Strong superbases can be designed by utilizing various approaches [7] [8] [9] to stabilize the conjugate acid, up to the theoretical limits of basicity. [10]
Organometallic superbases, sometimes called Lochmann–Schlosser superbases, result from the combination of alkali metal alkoxides and organolithium reagents. [11] Caubère defines superbases as "bases resulting from a mixing of two (or more) bases leading to new basic species possessing inherent new properties. The term superbase does not mean a base is thermodynamically and/or kinetically stronger than another, instead it means that a basic reagent is created by combining the characteristics of several different bases." [12]
Organic superbases are mostly charge-neutral, nitrogen containing species, where nitrogen act as a proton acceptor. These include the phosphazenes, phosphanes, amidines, and guanidines. Other organic compounds that meet the physicochemical or structural definitions of 'superbase' include proton chelators like the aromatic proton sponges and the bispidines. [14] [15] Multicyclic polyamines, like DABCO might also be loosely included in this category. [4] Phosphanes and carbodiphosphoranes are also strong organosuperbases. [16] [17] [18] [19]
Despite enormous proton affinity, many organosuperbases can exhibit low nucleophilicity.
Superbases are used in organocatalysis. [20] [21]
Organometallic compounds of electropositive metals are superbases, but they are generally strong nucleophiles. Examples include organolithium and organomagnesium (Grignard reagent) compounds. Another type of organometallic superbase has a reactive metal exchanged for a hydrogen on a heteroatom, such as oxygen (unstabilized alkoxides) or nitrogen (metal amides such as lithium diisopropylamide). [23]
The Schlosser base (or Lochmann-Schlosser base), the combination of n-butyllithium and potassium tert-butoxide, is commonly cited as a superbase. n-Butyllithium and potassium tert-butoxide form a mixed aggregate of greater reactivity than either component reagent. [24]
Inorganic superbases are typically salt-like compounds with small, highly charged anions, e.g. lithium hydride, potassium hydride, and sodium hydride. Such species are insoluble, but the surfaces of these materials are highly reactive and slurries are useful in synthesis. Caesium oxide is probably the strongest base according to quantum-chemical calculations. [10]
Pyrimidine is an aromatic, heterocyclic, organic compound similar to pyridine. One of the three diazines, it has nitrogen atoms at positions 1 and 3 in the ring. The other diazines are pyrazine and pyridazine.
In organometallic chemistry, organolithium reagents are chemical compounds that contain carbon–lithium (C–Li) bonds. These reagents are important in organic synthesis, and are frequently used to transfer the organic group or the lithium atom to the substrates in synthetic steps, through nucleophilic addition or simple deprotonation. Organolithium reagents are used in industry as an initiator for anionic polymerization, which leads to the production of various elastomers. They have also been applied in asymmetric synthesis in the pharmaceutical industry. Due to the large difference in electronegativity between the carbon atom and the lithium atom, the C−Li bond is highly ionic. Owing to the polar nature of the C−Li bond, organolithium reagents are good nucleophiles and strong bases. For laboratory organic synthesis, many organolithium reagents are commercially available in solution form. These reagents are highly reactive, and are sometimes pyrophoric.
1,8-Bis(dimethylamino)naphthalene is an organic compound with the formula C10H6(NMe2)2 (Me = methyl). It is classified as a peri-naphthalene, i.e. a 1,8-disubstituted derivative of naphthalene. Owing to its unusual structure, it exhibits exceptional basicity. It is often referred by the trade name Proton Sponge, a trademark of Sigma-Aldrich.
The Suzuki reaction is an organic reaction, classified as a cross-coupling reaction, where the coupling partners are a boronic acid and an organohalide and the catalyst is a palladium(0) complex. It was first published in 1979 by Akira Suzuki, and he shared the 2010 Nobel Prize in Chemistry with Richard F. Heck and Ei-ichi Negishi for their contribution to the discovery and development of palladium-catalyzed cross-couplings in organic synthesis. This reaction is also known as the Suzuki–Miyaura reaction or simply as the Suzuki coupling. It is widely used to synthesize polyolefins, styrenes, and substituted biphenyls. Several reviews have been published describing advancements and the development of the Suzuki reaction. The general scheme for the Suzuki reaction is shown below, where a carbon-carbon single bond is formed by coupling a halide (R1-X) with an organoboron species (R2-BY2) using a palladium catalyst and a base. The organoboron species is usually synthesized by hydroboration or carboboration, allowing for rapid generation of molecular complexity.
In chemistry, the term phosphonium describes polyatomic cations with the chemical formula PR+
4. These cations have tetrahedral structures. The salts are generally colorless or take the color of the anions.
Amidines are organic compounds with the functional group RC(NR)NR2, where the R groups can be the same or different. They are the imine derivatives of amides (RC(O)NR2). The simplest amidine is formamidine, HC(=NH)NH2.
1,8-Diazabicyclo[5.4.0]undec-7-ene, or more commonly DBU, is a chemical compound and belongs to the class of amidine compounds. It is used in organic synthesis as a catalyst, a complexing ligand, and a non-nucleophilic base.
Metalation is a chemical reaction that forms a bond to a metal. This reaction usually refers to the replacement of a halogen atom in an organic molecule with a metal atom, resulting in an organometallic compound. In the laboratory, metalation is commonly used to activate organic molecules during the formation of C—X bonds, which are necessary for the synthesis of many organic molecules.
The Hiyama coupling is a palladium-catalyzed cross-coupling reaction of organosilanes with organic halides used in organic chemistry to form carbon–carbon bonds. This reaction was discovered in 1988 by Tamejiro Hiyama and Yasuo Hatanaka as a method to form carbon-carbon bonds synthetically with chemo- and regioselectivity. The Hiyama coupling has been applied to the synthesis of various natural products.
n-Butyllithium C4H9Li (abbreviated n-BuLi) is an organolithium reagent. It is widely used as a polymerization initiator in the production of elastomers such as polybutadiene or styrene-butadiene-styrene (SBS). Also, it is broadly employed as a strong base (superbase) in the synthesis of organic compounds as in the pharmaceutical industry.
Hexamethylphosphoramide, often abbreviated HMPA, is a phosphoramide (an amide of phosphoric acid) with the formula [(CH3)2N]3PO. This colorless liquid is a useful reagent in organic synthesis.
Potassium hydride, KH, is the inorganic compound of potassium and hydrogen. It is an alkali metal hydride. It is a white solid, although commercial samples appear gray. It is a powerful superbase that is useful in organic synthesis. It is sold commercially as a slurry (~35%) in mineral oil or sometimes paraffin wax to facilitate dispensing.
Organozinc chemistry is the study of the physical properties, synthesis, and reactions of organozinc compounds, which are organometallic compounds that contain carbon (C) to zinc (Zn) chemical bonds.
Phosphazenes refer to classes of organophosphorus compounds featuring phosphorus(V) with a double bond between P and N. One class of phosphazenes have the formula R−N=P(−NR2)3. These phosphazenes are also known as iminophosphoranes and phosphine imides. They are superbases. Another class of compounds called phosphazenes are represented with the formula (−N=P 2−)n, where X = halogen, alkoxy group, amide and other organyl groups. One example is hexachlorocyclotriphosphazene (−N=P 2−)3. Bis(triphenylphosphine)iminium chloride [Ph3P=N=PPh3]+Cl−is also referred to as a phosphazene, where Ph = phenyl group. This article focuses on those phosphazenes with the formula R−N=P(−NR2)3.
Group 2 organometallic chemistry refers to the chemistry of compounds containing carbon bonded to any group 2 element. By far the most common group 2 organometallic compounds are the magnesium-containing Grignard reagents which are widely used in organic chemistry. Other organmetallic group 2 compounds are rare and are typically limited to academic interests.
Schlosser's base describes various superbasic mixtures of an alkyllithium compound and a potassium alkoxide. The reagent is named after Manfred Schlosser, although he uses the term LICKOR superbase. The superbasic nature of the reagent is a consequence of the in situ formation of the corresponding organopotassium compound, as well as changes to the aggregation state of the alkyllithium species.
Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. Organoiron compounds are relevant in organic synthesis as reagents such as iron pentacarbonyl, diiron nonacarbonyl and disodium tetracarbonylferrate. While iron adopts oxidation states from Fe(−II) through to Fe(VII), Fe(IV) is the highest established oxidation state for organoiron species. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals. Organoiron compounds feature a wide range of ligands that support the Fe-C bond; as with other organometals, these supporting ligands prominently include phosphines, carbon monoxide, and cyclopentadienyl, but hard ligands such as amines are employed as well.
Organosodium chemistry is the chemistry of organometallic compounds containing a carbon to sodium chemical bond. The application of organosodium compounds in chemistry is limited in part due to competition from organolithium compounds, which are commercially available and exhibit more convenient reactivity.
P4-t-Bu is a readily accessible chemical from the group of neutral, peralkylated sterically hindered polyaminophosphazenes, which are extremely strong bases but very weak nucleophiles, with the formula (CH3)3C−N=P(−N=P(−N(CH3)2)3)3. "t-Bu" stands for tert-butyl(CH3)3C–. "P4" stands for the fact that this molecule has 4 phosphorus atoms. P4-t-Bu can also be regarded as tetrameric triaminoiminophosphorane of the basic structure H−N=P(−NH2)3. The homologous series of P1 to P7 polyaminophosphazenes of the general formula with preferably methyl groups as R1, a methyl group or tert-butyl group as and even-numbered x between 0 and 6 (P4-t-Bu: R1 = Me, R2 = t-Bu and x = 3) has been developed by Reinhard Schwesinger; the resulting phosphazene bases are therefore also referred to as Schwesinger superbases.
7-Methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (mTBD) is a bicyclic strong guanidine base (pKa = 25.43 in CH3CN and pKa = 17.9 in THF). mTBD, like 1,5,7-triazabicyclo[4.4.0]dec-5-ene and other guanidine super bases, can be used as a catalyst in a variety of chemical reactions. It also reacts with CO2, which could make it useful for carbon capture and storage.
{{cite journal}}: CS1 maint: multiple names: authors list (link)