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Krische Allylation
The Krische allylation involves the enantioselective iridium-catalyzed addition of an allyl group to an aldehyde or an alcohol, resulting in the formation of a secondary homoallylic alcohol. The mechanism of the Krische allylation involves primary alcohol dehydrogenation or, when using aldehyde reactants, hydrogen transfer from 2-propanol. Unlike other allylation methods, the Krische allylation avoids the use of preformed allyl metal reagents and enables the direct conversion of primary alcohols to secondary homoallylic alcohols (precluding alcohol to aldehyde oxidation). Background Enantioselective carbonyl allylations are frequently applied to the synthesis of polyketide natural products. In 1978, Hoffmann reported the first asymmetric carbonyl allylation using a chiral allylmetal reagent, an allylborane derived from camphor. Subsequently, other chiral allylmetal reagents were developed by Kumada, Roush, Brown, Leighton, and others. These methods utilize preformed allyl meta ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Enantioselective
In chemistry, an enantiomer ( /ɪˈnænti.əmər, ɛ-, -oʊ-/ ''ih-NAN-tee-ə-mər''; from Ancient Greek ἐνάντιος ''(enántios)'' 'opposite', and μέρος ''(méros)'' 'part') – also called optical isomer, antipode, or optical antipode – is one of two stereoisomers that are non-superposable onto their own mirror image. Enantiomers are much like one's right and left hands, when looking at the same face, they cannot be superposed onto each other. No amount of reorientation will allow the four unique groups on the chiral carbon (see Chirality (chemistry)) to line up exactly. The number of stereoisomers a molecule has can be determined by the number of chiral carbons it has. Stereoisomers include both enantiomers and diastereomers. Diastereomers, like enantiomers, share the same molecular formula and are non-superposable onto each other however, they are not mirror images of each other. A molecule with chirality rotates plane-polarized light. A mixture of equals amou ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Borrowing Hydrogen (Hydrogen Auto-transfer)
Hydrogen auto-transfer, also known as borrowing hydrogen, is the activation of a chemical reaction by temporary transfer of two hydrogen atoms from the reactant to a catalyst and return of those hydrogen atoms back to a reaction intermediate to form the final product. Two major classes of borrowing hydrogen reactions exist: (a) those that result in hydroxyl substitution, and (b) those that result in carbonyl addition. In the former case, alcohol dehydrogenation generates a transient carbonyl compound that is subject to condensation followed by the return of hydrogen. In the latter case, alcohol dehydrogenation is followed by reductive generation of a nucleophile, which triggers carbonyl addition. As borrowing hydrogen processes avoid manipulations otherwise required for discrete alcohol oxidation and the use of stoichiometric organometallic reagents, they typically display high levels of atom-economy and, hence, are viewed as examples of Green chemistry. History The Guerbet react ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Precatalyst
In chemistry, a catalytic cycle is a multistep reaction mechanism that involves a catalyst. The catalytic cycle is the main method for describing the role of catalysts in biochemistry, organometallic chemistry, bioinorganic chemistry, materials science, etc. Since catalysts are regenerated, catalytic cycles are usually written as a sequence of chemical reactions in the form of a loop. In such loops, the initial step entails binding of one or more reactants by the catalyst, and the final step is the release of the product and regeneration of the catalyst. Articles on the Monsanto process, the Wacker process, and the Heck reaction show catalytic cycles. A catalytic cycle is not necessarily a full reaction mechanism. For example, it may be that the intermediates have been detected, but it is not known by which mechanisms the actual elementary reactions occur. Precatalysts Precatalysts are not catalysts but are ''precursors'' to catalysts. Precatalysts are converted in the react ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Catalytic Cycle
In chemistry, a catalytic cycle is a multistep reaction mechanism that involves a catalyst. The catalytic cycle is the main method for describing the role of catalysts in biochemistry, organometallic chemistry, bioinorganic chemistry, materials science, etc. Since catalysts are regenerated, catalytic cycles are usually written as a sequence of chemical reactions in the form of a loop. In such loops, the initial step entails binding of one or more reactants by the catalyst, and the final step is the release of the product and regeneration of the catalyst. Articles on the Monsanto process, the Wacker process, and the Heck reaction show catalytic cycles. A catalytic cycle is not necessarily a full reaction mechanism. For example, it may be that the intermediates have been detected, but it is not known by which mechanisms the actual elementary reactions occur. Precatalysts Precatalysts are not catalysts but are ''precursors'' to catalysts. Precatalysts are converted in the react ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Scheme 5 MJK
A scheme is a systematic plan for the implementation of a certain idea. Scheme or schemer may refer to: Arts and entertainment * ''The Scheme'' (TV series), a BBC Scotland documentary series * The Scheme (band), an English pop band * ''The Scheme'', an action role-playing video game for the PC-8801, made by Quest Corporation * Schemer (comics), Richard Fisk, a Marvel Comics villain turned antihero * Horace Schemer, a fictional character in the TV series ''Shining Time Station'' * Schemee, a fictional child character and Schemer's nephew in the TV Series ''Shining Time Station'' * ''Schemers'' (film), a Scottish film Other uses * Classification scheme, eg a thesaurus, a taxonomy, a data model, or an ontology * Scheme (programming language), a minimalist dialect of Lisp * Scheme (mathematics), a concept in algebraic geometry * Scheme (linguistics), a figure of speech that changes a sentence's structure * Scam, an attempt to swindle or cheat people through deception **Get-rich-quic ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Scheme 4 MJK
A scheme is a systematic plan for the implementation of a certain idea. Scheme or schemer may refer to: Arts and entertainment * ''The Scheme'' (TV series), a BBC Scotland documentary series * The Scheme (band), an English pop band * ''The Scheme'', an action role-playing video game for the PC-8801, made by Quest Corporation * Schemer (comics), Richard Fisk, a Marvel Comics villain turned antihero * Horace Schemer, a fictional character in the TV series ''Shining Time Station'' * Schemee, a fictional child character and Schemer's nephew in the TV Series ''Shining Time Station'' * ''Schemers'' (film), a Scottish film Other uses * Classification scheme, eg a thesaurus, a taxonomy, a data model, or an ontology * Scheme (programming language), a minimalist dialect of Lisp * Scheme (mathematics), a concept in algebraic geometry * Scheme (linguistics), a figure of speech that changes a sentence's structure * Scam, an attempt to swindle or cheat people through deception **Get-rich-quic ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Scheme 3 MJK
A scheme is a systematic plan for the implementation of a certain idea. Scheme or schemer may refer to: Arts and entertainment * ''The Scheme'' (TV series), a BBC Scotland documentary series * The Scheme (band), an English pop band * ''The Scheme'', an action role-playing video game for the PC-8801, made by Quest Corporation * Schemer (comics), Richard Fisk, a Marvel Comics villain turned antihero * Horace Schemer, a fictional character in the TV series ''Shining Time Station'' * Schemee, a fictional child character and Schemer's nephew in the TV Series ''Shining Time Station'' * ''Schemers'' (film), a Scottish film Other uses * Classification scheme, eg a thesaurus, a taxonomy, a data model, or an ontology * Scheme (programming language), a minimalist dialect of Lisp * Scheme (mathematics), a concept in algebraic geometry * Scheme (linguistics), a figure of speech that changes a sentence's structure * Scam, an attempt to swindle or cheat people through deception **Get-rich-quic ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Allyl Acetate
Allyl acetate is an organic compound with formula C3H5OC(O)CH3. This colourless liquid is a precursor to especially allyl alcohol, which is a useful industrial intermediate. It is the acetate ester of allyl alcohol. Preparation Allyl acetate is produced industrially by the gas phase reaction of propene in the presence of acetic acid using a palladium catalyst: :C3H6 + CH3COOH + ½ O2 → CH2=CHCH2OCOCH3 + H2O This method is advantageous because propene is inexpensive and "green." Allyl alcohol is also produced primarily from allyl chloride, but production via the hydrolysis of allyl acetate route avoids the use of chlorine, and so is increasing in use. Vinyl acetate is produced similarly, using ethylene in place of propene. These reactions are examples of acetoxylation. The palladium center is then re-oxidized by the O2 present. The mechanism for the acetoxylation follows a similar pathway, with propene forming a π-allyl bond on the palladium. : Reactions and applicatio ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Scheme 2 MJK
A scheme is a systematic plan for the implementation of a certain idea. Scheme or schemer may refer to: Arts and entertainment * ''The Scheme'' (TV series), a BBC Scotland documentary series * The Scheme (band), an English pop band * ''The Scheme'', an action role-playing video game for the PC-8801, made by Quest Corporation * Schemer (comics), Richard Fisk, a Marvel Comics villain turned antihero * Horace Schemer, a fictional character in the TV series ''Shining Time Station'' * Schemee, a fictional child character and Schemer's nephew in the TV Series ''Shining Time Station'' * ''Schemers'' (film), a Scottish film Other uses * Classification scheme, eg a thesaurus, a taxonomy, a data model, or an ontology * Scheme (programming language), a minimalist dialect of Lisp * Scheme (mathematics), a concept in algebraic geometry * Scheme (linguistics), a figure of speech that changes a sentence's structure * Scam, an attempt to swindle or cheat people through deception **Get-rich-quic ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Racemization
In chemistry, racemization is a conversion, by heat or by chemical reaction, of an optically active compound into a racemic (optically inactive) form. This creates a 1:1 molar ratio of enantiomers and is referred too as a racemic mixture (i.e. contain equal amount of (+) and (−) forms). Plus and minus forms are called Dextrorotation and levorotation. The D and L enantiomers are present in equal quantities, the resulting sample is described as a racemic mixture or a racemate. Racemization can proceed through a number of different mechanisms, and it has particular significance in pharmacology as different enantiomers may have different pharmaceutical effects. Stereochemistry Chiral molecules have two forms (at each point of asymmetry), which differ in their optical characteristics: The ''levorotatory form'' (the ''(−)-form'') will rotate counter-clockwise on the plane of polarization of a beam of light, whereas the ''dextrorotatory'' form (the ''(+)-form'') will rotate clockw ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Chirality
Chirality is a property of asymmetry important in several branches of science. The word ''chirality'' is derived from the Greek (''kheir''), "hand", a familiar chiral object. An object or a system is ''chiral'' if it is distinguishable from its mirror image; that is, it cannot be superimposed onto it. Conversely, a mirror image of an ''achiral'' object, such as a sphere, cannot be distinguished from the object. A chiral object and its mirror image are called ''enantiomorphs'' (Greek, "opposite forms") or, when referring to molecules, '' enantiomers''. A non-chiral object is called ''achiral'' (sometimes also ''amphichiral'') and can be superposed on its mirror image. The term was first used by Lord Kelvin in 1893 in the second Robert Boyle Lecture at the Oxford University Junior Scientific Club which was published in 1894: Human hands are perhaps the most recognized example of chirality. The left hand is a non-superimposable mirror image of the right hand; no matter ho ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Protecting Group
A protecting group or protective group is introduced into a molecule by chemical modification of a functional group to obtain chemoselectivity in a subsequent chemical reaction. It plays an important role in multistep organic synthesis. In many preparations of delicate organic compounds, some specific parts of their molecules cannot survive the required reagents or chemical environments. Then, these parts, or groups, must be protected. For example, lithium aluminium hydride is a highly reactive but useful reagent capable of reducing esters to alcohols. It will always react with carbonyl groups, and this cannot be discouraged by any means. When a reduction of an ester is required in the presence of a carbonyl, the attack of the hydride on the carbonyl has to be prevented. For example, the carbonyl is converted into an acetal, which does not react with hydrides. The acetal is then called a protecting group for the carbonyl. After the step involving the hydride is complete, the acet ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
