Allylation amines

Allyl amine Allyl cyanide Allyl ether Allyl halide Amines... 

A wide range of carbon, nitrogen, and oxygen nucleophiles react with allylic esters in the presence of iridium catalysts to form branched allylic substitution products. The bulk of the recent literature on iridium-catalyzed allylic substitution has focused on catalysts derived from [Ir(COD)Cl]2 and phosphoramidite ligands. These complexes catalyze the formation of enantiomerically enriched allylic amines, allylic ethers, and (3-branched y-8 unsaturated carbonyl compounds. The latest generation and most commonly used of these catalysts (Scheme 1) consists of a cyclometalated iridium-phosphoramidite core chelated by 1,5-cyclooctadiene. A fifth coordination site is occupied in catalyst precursors by an additional -phosphoramidite or ethylene. The phosphoramidite that is used to generate the metalacyclic core typically contains one BlNOLate and one bis-arylethylamino group on phosphorus. 

Palladium-catalyzed, Allylic Amination. Allylic substitution of mono-saccharidic hex-2-enopyranoside 4-acetates with secondary amines in the presence of tetrakis (triphenylphosphine)palladium(O) liad led to a large variety of 4-aminated 2-enosides, with retention of configuration (56-58). The method was applied to the disaccaridic enoside 1 to give, with benzylmethylamine or dibenzylamine, the 4-amino sugar derivatives g in yields of 92 and 67% (46). Studies concerning hydrox-ylation of t)ie double bond and subsequent deprotection are incomplete. 

Allyl amines, allyl thioethers, and allylferrocenylselenide react analogously with butatrienylidene complex 10 by initial addition to C3 and subsequent hetero-Cope or hetero-Claisen rearrangement (Scheme 3.23) [21, 42-45]. 

The basic Markovnikov selectivity pattern is partially or fully overrun in the presence of neighboring coordinating groups within the olefin substrate (Section 2.2.2). Known functionalities where inversed selectivity can occur include 3-alke-noylamides (e.g. 17 reacts to give a mixture of 18 and 19, Table 3) [43], homoallyl esters and alcohols, allyl ethers (but not necessarily allyl alcohols) [44], allyl amines, allyl amides, or carbamates (cf. 20 to 21) [45], allyl sulfides [46] or 1,5-dienes [47]. As a matter of fact, aldehyde by-products are quite normal in Wacker reactions, but tend to be overlooked. 

The second approach for the nucleophilic animation reactions to be considered here will be reactions of allyl halides and allyl acetates leading to allyl amines. Allyl halides are normally very reactive in SN2 reactions, but the direct coupling of allyl halides with nitrogen nucleophiles has been performed with limited success [4], as di- and trialkylated by products often predominate. The application of the Gabriel synthesis can to a certain extent eliminate the problem with polyalkylation of amines using, e.g., the stabilized phthalimide anion 19 as the nucleophile. The allyl amine 20... 

Xanthene-phosphole ligands in the palladium-catalyzed amine allylation <20070M1846>. 

Oxidation of alcohols and amines. Allylic and benzylic alcohols can be oxidized to the aldehydes in high yield by oxygen in the presence of catalytic amounts of 1 and... 

AUylic amines. Allylic phenyl selenides on reaction with NCS (excess), an alkyl carbamate, and triethylamine at room temperature are converted into the corresponding rearranged carbamate-protected primary allylic amines. 

Amin Allyl-benzyl- IV/ld, 350 -Hydrochlorid E16d, 709 (N-Allyiierung)... 

Allylic alcohols are reduced with lithium or sodium in ammonia, or low molecular weight amines either with or without alcohols. The thermodynamically more stable product is often formed, leading to rearrangement in some cases (equation 71). Methyl and cyclic ethers are similarly reduced (equations 72 and 73), as are allylic acetates, halides and epoxides (equation 74 and 75). 7.i08 Benzylic and allylic sulfides and sulfones are readily reduced to hydrocarbons using lithium or sodium in alcoholic solvents or in amines. " Allylic sulfones are reduced in a similar manner (Scheme 11)," either with or without migration of the double bond, depending on the reaction conditions used. 

Regioselectivity Anions of allyl silanes Anions of allyl sulfides Anions of allyl ethers Anions of allyl amines Asymmetric allylic amines Allyl Carbamates... 

Borohydride reduced Pd is also a versatile hydrogenation catalyst that effects the partial reduction of multifunctional unsaturated compounds selectively. It can reduce the w-bond of C=C, N=N, N=0, but not the w-bond of C=N, C=0, nor the --bond of C— N, C—O. Allylic alcohols, allylic amines, allylic ethers, a-methylstyrene, acrylamide, 3-butene nitro, and also mesityl oxide, crotonaldehyde, and maleic anhydride are among the selectively reduced substrates. ... 

NITRIC ACID (7697-37-2) A strong acid and oxidizer. Reacts with water or steam, forming toxic and corrosive nitrous fumes. Violent reaction when water is added to concentrated acid. To dilute, always add acid to water heat will be generated. Reacts violently with reducing agents, bases, combustible materials, finely dispersed or powdered metals and metal alloys, acetic anhydride, acetone, acetylene, acrolein, acrylonitrile, alcohols, aliphatic amines, allyl chloride, ammonia, aniline, anion exchange resins, 1,4-benzoquinone diimine,... 

The Buchwald series of bulky phosphines containing the tunable bi-aryl moiety have also been shown to allow for the efficient animation of aryl chlorides as well.57 In particular, Pd/L3 catalyzed the reaction between secondary cyclic amines and most aryl chlorides at 80 °C, Secondary acyclic amines and anilines tend to couple best with neutral to electron rich aryl chlorides. Primary aliphatic amines are quite limited to either the amination of o-tolyl chlorides, or more activated primary amines such as benzyl amine. A better ligand for this transformation was reported to be L4 as the amination could be conducted at room temperature in many cases.58 Base sensitive R1 required the use of K3PO4 rather than NaOf-Bu. Most amines work well with this catalyst system, except for unactivated primary aliphatic amines (e.g., n-hexyl amine). Allyl amine, hydrazines, imines, benzyl amine, and (EtO)2CH2NH2 all couple well with aryl chlorides under the... 

Aminations. Allylic amu made up of Ru3(CO)i2 and a his Aromatic ketimines are fori Interestingly, styrenes afford ad... 

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