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Non-nucleophilic Base
As the name suggests, a non-nucleophilic base is a sterically hindered organic base that is a poor nucleophile. Normal bases are also nucleophiles, but often chemists seek the proton-removing ability of a base without any other functions. Typical non-nucleophilic bases are bulky, such that protons can attach to the basic center but alkylation and complexation is inhibited. Non-nucleophilic bases A variety of amines and nitrogen heterocycles are useful bases of moderate strength (pKa of conjugate acid * ''N'',''N''-Diisopropylethylamine (DIPEA, also called Hünig's Base), p *1,8-Diazabicycloundec-7-ene (DBU) - useful for E2 elimination reactions, pKa = 13.5 * 1,5-Diazabicyclo(4.3.0)non-5-ene (DBN) - comparable to DBU * 2,6-Di-tert-butylpyridine, a weak non-nucleophilic base pKa = 3.58 * Phosphazene bases, such as t-Bu-P4''Activation in anionic polymerization: Why phosphazene bases are very exciting promoters'' S. Boileau, N. Illy Prog. Polym. Sci., 2011, 36, 1132-1151, {{doi, 10. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Steric Effects
Steric effects arise from the spatial arrangement of atoms. When atoms come close together there is a rise in the energy of the molecule. Steric effects are nonbonding interactions that influence the shape ( conformation) and reactivity of ions and molecules. Steric effects complement electronic effects, which dictate the shape and reactivity of molecules. Steric repulsive forces between overlapping electron clouds result in structured groupings of molecules stabilized by the way that opposites attract and like charges repel. Steric hindrance Steric hindrance is a consequence of steric effects. Steric hindrance is the slowing of chemical reactions due to steric bulk. It is usually manifested in ''intermolecular reactions'', whereas discussion of steric effects often focus on ''intramolecular interactions''. Steric hindrance is often exploited to control selectivity, such as slowing unwanted side-reactions. Steric hindrance between adjacent groups can also affect torsional ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Potassium Bis(trimethylsilyl)amide
Potassium bis(trimethylsilyl)amide (commonly abbreviated as KHMDS, Potassium(K) HexaMethylDiSilazide) or potassium hexamethyldisilazane is the chemical compound with the formula ((CH3)3Si)2NK. It is a strong, non-nucleophilic base with an approximate pKa of 26 (compare to lithium diisopropylamide, at 36). Structure In the solid state, the unsolvated compound is dimeric, with two potassium and two nitrogen atoms forming a square. This compound is soluble in hydrocarbon solvents and conducts electricity poorly in solution and in the melt. This is attributed to very strong ion pairing.{{cite journal , doi = 10.1021/ic00333a029 , journal = Inorg. Chem. , title = Ion pairing in is(trimethylsilyl)amidootassium: The x-ray crystal structure of unsolvated N(SiMe3)2 , year = 1990 , last1 = Tesh , first1 = Kris F. , last2 = Hanusa , first2 = Timothy P. , last3 = Huffman , first3 = John C. , volume = 29 , issue = 8 , pages = 1584–1586 See also * Metal bis(trimethylsilyl)amid ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Claisen Condensation
The Claisen condensation is a carbon–carbon bond forming reaction that occurs between two esters or one ester and another carbonyl compound in the presence of a strong base, resulting in a β-keto ester or a β-diketone. It is named after Rainer Ludwig Claisen, who first published his work on the reaction in 1887. Requirements At least one of the reagents must be enolizable (have an α-proton and be able to undergo deprotonation to form the enolate anion). There are a number of different combinations of enolizable and nonenolizable carbonyl compounds that form a few different types of Claisen. The base used must not interfere with the reaction by undergoing nucleophilic substitution or addition with a carbonyl carbon. For this reason, the conjugate sodium alkoxide base of the alcohol formed (e.g. sodium ethoxide if ethanol is formed) is often used, since the alkoxide is regenerated. In mixed Claisen condensations, a non-nucleophilic base such as lithium diisopropylamide, or L ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Enol
In organic chemistry, alkenols (shortened to enols) are a type of reactive structure or intermediate in organic chemistry that is represented as an alkene ( olefin) with a hydroxyl group attached to one end of the alkene double bond (). The terms ''enol'' and ''alkenol'' are portmanteaus deriving from "-ene"/"alkene" and the "-ol" suffix indicating the hydroxyl group of alcohols, dropping the terminal "-e" of the first term. Generation of enols often involves removal of a hydrogen adjacent (α-) to the carbonyl group—i.e., deprotonation, its removal as a proton, . When this proton is not returned at the end of the stepwise process, the result is an anion termed an enolate (see images at right). The enolate structures shown are schematic; a more modern representation considers the molecular orbitals that are formed and occupied by electrons in the enolate. Similarly, generation of the enol often is accompanied by "trapping" or masking of the hydroxy group as an ether, such as ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Ester
In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides are fatty acid esters of glycerol; they are important in biology, being one of the main classes of lipids and comprising the bulk of animal fats and vegetable oils. Esters typically have a pleasant smell; those of low molecular weight are commonly used as fragrances and are found in essential oils and pheromones. They perform as high-grade solvents for a broad array of plastics, plasticizers, resins, and lacquers, and are one of the largest classes of synthetic lubricants on the commercial market. Polyesters are important plastics, with monomers linked by ester moieties. Phosphoesters form the backbone of DNA molecules. Nitrate esters, such as nitroglycerin, are known for their explosive properties. '' Nomenclature Etymology Th ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Deprotonation
Deprotonation (or dehydronation) is the removal (transfer) of a proton (or hydron, or hydrogen cation), (H+) from a Brønsted–Lowry acid in an acid–base reaction.Henry Jakubowski, Biochemistry Online Chapter 2A3, https://employees.csbsju.edu/hjakubowski/classes/ch331/protstructure/PS_2A3_AA_Charges.html, accessed 12/2/2020 The species formed is the conjugate base of that acid. The complementary process, when a proton is added (transferred) to a Brønsted–Lowry base, is protonation (or hydronation). The species formed is the conjugate acid of that base. A species that can either accept or donate a proton is referred to as amphiprotic. An example is the H2O (water) molecule, which can gain a proton to form the hydronium ion, H3O+, or lose a proton, leaving the hydroxide ion, OH−. The relative ability of a molecule to give up a proton is measured by its p''K''a value. A low p''K''a value indicates that the compound is acidic and will easily give up its proton to a base ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Lithium Diisopropylamide
Lithium diisopropylamide (commonly abbreviated LDA) is a chemical compound with the molecular formula . It is used as a strong base and has been widely utilized due to its good solubility in non-polar organic solvents and non-nucleophilic nature. It is a colorless solid, but is usually generated and observed only in solution. It was first prepared by Hamell and Levine in 1950 along with several other hindered lithium diorganylamides to effect the deprotonation of esters at the α position without attack of the carbonyl group. Preparation and structure LDA is commonly formed by treating a cooled (0 to −78 °C) mixture of tetrahydrofuran and diisopropylamine with ''n''-butyllithium. When dissociated, the diisopropylamide anion can become protonated to form diisopropylamine. Diisopropylamine has a p''K''a value of 36. Therefore, its conjugate base is suitable for the deprotonation of compounds with greater acidity, importantly, such weakly acidic compounds (carbon acids) ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Potassium Tert-butoxide
Potassium ''tert''-butoxide is the chemical compound with the formula K+(CH3)3CO−. This colourless solid is a strong base (pKa of conjugate acid around 17), which is useful in organic synthesis. It exists as a tetrameric cubane-type cluster. It is often seen written in chemical literature as potassium ''t''-butoxide. The compound is often depicted as a salt, and it often behaves as such, but it is not ionized in solution. Preparation Potassium ''t''-butoxide is commercially available as a solution and as a solid, but it is often generated ''in situ'' for laboratory use because samples are so sensitive and older samples are often of poor quality. It is prepared by the reaction of dry ''tert''-butyl alcohol with potassium metal. The solid is obtained by evaporating these solutions followed by heating the solid. The solid can be purified by sublimation at 220 °C and 1 mmHg. Sublimation can also take place at 140 °C and 0.01 hPa. It is advisable to cover the ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Sodium Tert-butoxide
Sodium ''tert''-butoxide is the chemical compound with the formula (CH3)3CONa. It is a strong base and a non-nucleophilic base. It is flammable and moisture sensitive. It is sometimes written in chemical literature as sodium ''t''-butoxide. It is similar in reactivity to the more common potassium ''tert''-butoxide. The compound can be produced by treating ''tert''-butyl alcohol with sodium hydride. Reactions One application for sodium ''tert''-butoxide is as a non-nucleophilic base. It has been widely used in the Buchwald–Hartwig amination, as in this typical example: Sodium tert-butoxide is used to prepare tert-butoxide complexes. For example hexa(tert-butoxy)ditungsten(III) is thus converted by the salt metathesis reaction from a ditungsten heptachloride: :NaW2Cl7(THF)5 + 6 NaOBu-t → W2(OBu-t)6 + 7 NaCl + 5 THF Structure Sodium ''tert''-butoxide forms clusters in the solid state, both hexamers and nonamers. {, class="wikitable" style="text-align:center;" , ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Potassium Hydride
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. Preparation Potassium hydride is produced by direct combination of the metal and hydrogen: : This reaction was discovered by Humphry Davy soon after his 1807 discovery of potassium, when he noted that the metal would vaporize in a current of hydrogen when heated just below its boiling point.Humphry Davy (1808), ''The Bakerian Lecture on some new phenomena of chemical changes produced by electricity, particularly the decomposition of fixed alkalies, and the exhibition of the new substances which constitute their bases; and on the general nature of alkaline bodies.'' Philosophical Transactions of the Royal Society, volume 88, pages 1–44. In ''Th ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Sodium Hydride
Sodium hydride is the chemical compound with the empirical formula Na H. This alkali metal hydride is primarily used as a strong yet combustible base in organic synthesis. NaH is a saline (salt-like) hydride, composed of Na+ and H− ions, in contrast to molecular hydrides such as borane, methane, ammonia, and water. It is an ionic material that is insoluble in organic solvents (although soluble in molten Na), consistent with the fact that H− ions do not exist in solution. Because of the insolubility of NaH, all reactions involving NaH occur at the surface of the solid. Basic properties and structure NaH is produced by the direct reaction of hydrogen and liquid sodium.Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. . Pure NaH is colorless, although samples generally appear grey. NaH is ca. 40% denser than Na (0.968 g/cm3). NaH, like LiH, KH, RbH, and CsH, adopts the NaCl crystal structure. In this motif, each Na+ ion is surrounded by six H ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Lithium Tetramethylpiperidide
Lithium tetramethylpiperidide (often abbreviated LiTMP or LTMP) is a chemical compound with the molecular formula . It is used as a non-nucleophilic base, being comparable to LiHMDS in terms of steric hindrance. Synthesis It is synthesised by the deprotonation of 2,2,6,6-tetramethylpiperidine with ''n''-butyllithium at −78 °C. Recent reports show that this reaction can also be performed 0 °C. The compound is stable in a THF/ethylbenzene solvent mixture and is commercially available as such. Structure Like many lithium reagents it has a tendency to aggregate, forming a tetramer in the solid state. See also *Lithium diisopropylamide *Lithium amide Lithium amide or lithium azanide is an inorganic compound with the chemical formula . It is a white solid with a tetragonal crystal structure. Lithium amide can be made by treating lithium metal with liquid ammonia: : Other lithium amides The co ... References {{Lithium compounds Lithium compounds Non-nucleophilic bases ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
