Phosphine imines amines

Abstract This chapter principally concerns oxidations of organic substrates containing N, O, S, P, As and Sb. Oxidations of amines are covered first, including primary amines to nitriles or amides secondary amines to imines or other products tertiary amines to N-oxides or other prodncts (Section 5.1) and the oxidation of amides (5.2). Oxidation of ethers to esters or lactones follows (5.3), then of sulfides to sulfoxides or sulfones (5.4) and of phosphines, arsine and stibines to their oxides (5.5). A final section (5.6) concerns such miscellaneous oxidations not covered by other sections in the book. 

Cyclometalation is one of the most reliable and versatile methods for the synthesis of stable Pd-C a-bonds. In this reaction, a palladium (or other metal) complex is reacted with a ligand possessing a donor atom. The metal is directed by the donor atom to insert into a C-H bond, forming a chelate ring. This donor is usually the nitrogen of a tertiary amine, heterocyclic amine, or imine, or a phosphorus in a tertiary phosphine or phosphite. Other donor atoms, such as O and S, are occasionally encountered. The chelate ring size is normally five. ... 

In addition, manganese oxide oxidizes benzylic methyl or methylene to carbonyl [814] and cleaves the carbon bonds of vicinal diols [577, 522]. It converts amines into imines [577, 525] tertiary amines into secondary amines [572], formamides [526, 527, 525], or ketones aromatic primary amines [575, 525] and hydrazo compounds [525] into azo compounds hy-droxylamines into nitroso [576] or nitro compounds [525] hydrazones into diazo compounds [520] phosphines into phosphine oxides [575] thiols into disulfides [576] and sulfides into sulfoxides [541]. 

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... 

In the area of 5 -di- and tri-phosphates, ATP, GTP, UTP and CTP, with deuterium in all of the 3 -, 4 -, and 5 -positions, have been made enzymically from the labelled ribose (Chapter 2) whilst chemical routes to the 5 -triphosphates of 4-thiouridine, 2-thiocytidine, 5-bromocytidine and [6- N]-adenosine have been described. Azidonucleosides can be converted by treatment with a polystyryl diphenylphosphine into polymer-bound phosphine imines (Vol. 28, p. 272) it has now been reported that the nucleoside phosphine imine can be converted to its 5 -triphosphate before hydrolysis to give the amine. The method was used to convert AZT into the 5 -triphosphate of 3 -amino-3 -deoxythymidine, amongst other cases.A method previously used to make the P -methyl-... 

P,N-Phosphine imine complexes of iridium (25) have also proved to be successful in intramolecular reactivity to give indole products, and intermolecular tandem catalytic routes have been developed to complete hydroamination/hydrosilylation sequences to realize secondary amine syntheses upon workup (Scheme 15.27) [188]. In this case, the Markovnikov products are obtained and enhanced catalyst efficiency is realized in the presence of weakly coordinating anions such as... 

Other allylic substrates have become useful allylic sources to synthesize palladium(ll) 77 -allyls by oxidative addition to Pd(0) complexes. Allylic nitrogen derivatives such as ammonium, pyridinium, iminium salts,and other derivatives have been used. Allyl phosphonium salts and allyl phosphates also lead to 7 -allylic palladium(n) complexes. In these examples, a bidentate ligand is present in the reaction medium either coordinated to the Pd(0) precursor or added to the reaction mixture, so the amine, pyridine, imine, or phosphine byproduct does not remain coordinated to the metal in the final rf-MyX complex. 

Ligand A anionic (e.g., halides, pseudohalides, alkyl, aryl, thiolate, alkoxide) ligand N neutral (e.g., amines, imines, phosphines, carbenes, nitriles, isonitriles, NO, CO) ligand C cationic (e.g., NO+)... 

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