Amines allyl esters

Transfer to monomer is of particular importance during the polymerization of allyl esters (113, X=()2CR), ethers (113, X=OR), amines (113, X=NR2) and related monomcrs.iw, 8, lb2 The allylic hydrogens of these monomers arc activated towards abstraction by both the double bond and the heteroatom substituent (Scheme 6.31). These groups lend stability to the radical formed (114) and are responsible for this radical adding monomer only slowly. This, in turn, increases the likelihood of side reactions (i.e. degradative chain transfer) and causes the allyl monomers to retard polymerization. 

DKR requires two catalysts one for resolution and one for racemization. We and others have developed a novel strategy using enzyme as the resolution catalyst and metal as the racemization catalyst as shown in Scheme 1. The R-selecfive DKR can be achieved by combining a R-selective enzyme with a proper metal catalyst and its counterpart by the combination of the metal catalyst with a -selective enzyme. This strategy has been demonstrated to be applicable to the DKR of secondary alcohols, allylic esters, and primary amines. Among them, the DKR of secondary alcohols has been the most successful. 

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. 

Addition to linear 1,1-disubstituted allylic acetates is slower than addition to monosubstituted allylic esters. Additions to allylic trifluoroacetates or phosphates are faster than additions to allylic carbonates or acetates, and reactions of branched allylic esters are faster than additions to linear allylic esters. Aryl-, vinyl, alkynyl, and alkyl-substituted allylic esters readily undergo allylic substitution. Amines and stabilized enolates both react with these electrophiles in the presence of the catalyst generated from an iridium precursor and triphenylphosphite. 

Another method for deallylation of allyl esters is the transfer of the allyl group to reactive nucleophiles. Amines such as morpholine are used[415-417], Potassium salts of higher carboxylic acids are used as an accepter of the allyl group[418]. The method is applied to the protection and deprotection of the acid function in rather unstable /3-lactam 664[419,420]. 

Allyl chloride is used to make intermediates for downstream derivatives such as resins and polymers. Approximately 90% of allyl chloride production is used to synthesize epichlorohydrin, which is used as a basic building block for epoxy resins and in glycerol synthesis. Allyl chloride is also a starting material for allyl ethers of phenols, bisphenol A and phenolic resins, and for some allyl esters. Other compounds made from allyl chloride are quaternary amines used in chelating agents and quaternary ammonium salts, which are used in water clarification and sewage sludge flocculation (Kneupper Saathoff, 1993). 

Most of these procedures are incompatible with common linkers, and are therefore unsuitable for the transformation of support-bound substrates into carboxylic acids. A more versatile approach for this purpose is the saponification of carboxylic esters. Saponifications with KOH or NaOH usually proceed smoothly on hydrophilic supports, such as Tentagel [19] or polyacrylamides, but not on cross-linked polystyrene. Esters linked to hydrophobic supports are more conveniently saponified with LiOH [45] or KOSiMe3 in THF or dioxane (Table 13.11). Alternatively, palladium(O)-mediated saponification of allyl esters [94] can be used to prepare acids on cross-linked polystyrene (Entries 9 and 10, Table 13.11). Fmoc-protected amines are not deprotected under these conditions [160],... 

Cholic acid and 3-phenylcarbamoyl cholic acid allyl esters were grafted to hydride-activated silica gel and the developed CSPs were used for the chiral resolution of derivatized amino acids, amines, alcohols, hydantoins, and 2,2 -... 

Hebach and Kazmaier reported the synthesis of cyclic peptidomimetics containing an alkylated amino acid via Ugi-4CR of N-terminal-protected aloc-amino acids, allyl isocyanoacetate, and chiral amines in trifluoroethanol. Allylic esters of tripeptides 193 were obtained in high yields and good stereoselectivity. Metathesis with 5% of Grubbs first-generation catalyst gave 16-membered cyclic peptides 194 in 30-50% yield (Scheme 2.69) [101]. 

K. Shiga, N. Iridium complex-catalyzed allylic amination of allylic esters./. Am. Chem. Soc. 2001, 123, 9525-9534. 

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. 

In terms of functional group compatibility, ethers, alcohols, tertiary amines, acetals, esters, amides and heterocycles are compatible with the Pauson-Khand reaction. In the intramolecular version, relatively few carbon skeletons undergo the cyclization. Most intramolecular PKRs use systems derived from hept-l-en-6-yne (6) or propargyl allyl ethers (7) or amines (8). Other interesting and more recent substrates are enynes connected through aromatic rings like 9-11, which have allowed us and other groups to obtain aromatic polycycles (Fig. 1) [28-31]. 

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