From unsaturated amines

Carbonylation. Insertion of CO 1 from unsaturated amines as well lyl)ethynes are realized in the presenc a-Siloxy aldehydes. The concur aldehydes by R jSiH and CO proceeds ai complex Rh(cod>2BF4 catalyzes hydros ( )-y-silyl allylic alcohols. ... 

Carbonylation. Insertion of CO into a C-S bond, and formation of lactams from unsaturated amines as well as indanones from l-aryl-2-(trimethylsi-lyl)ethynes" are realized in the presence of [Rh(cod)Cl]2. 

Carbamates. The Boc group is suitable for amine protection in hydroboration eactions. Thus, amino alcohols are synthesized from unsaturated amines via the IV-Boc aerivatives. The cleavage is effected with basic hydrogen peroxide. 

The catalyst formed dien oxygen is added to copper(I) chloride in pyridine has found considerable utility in the oxidation of a large number of nitrogen compounds. The preparation of unsaturated nitriles from unsaturated amines can be accomplished in a catalytic manner using cuprous chloride in pyridine [IS]. The oxidative cleavage of o-phenylenediamine catalyzed by cuprous chloride in pyridine takes place at room temperature to give cu,cis-mucononitrile, equation (113) [152]. 

Alkylation of cyclohexylidinephenylacetonitrile (89) with 2-chloroethyldimethylamine, using NaH as base, gives nitrile 90. Note that the product results from alkylation of the enolate which results in a double bond shift. This product (90) is transformed to unsaturated amine 91 on heating with HC1. 

Hydroformylation of unsaturated amines offer a convenient synthetic access to cyclic AT.O-hemiacetals. If performed in the presence of alcohols or orthoesters AT,O-acetals are formed. With additional N-nucleophiles N,N-acetals are obtained. These compounds are synthetically attractive building blocks and were therefore used as a key step in the synthesis of various natural products [27,35]. Thus the synthesis of (+)-prosopinine starting from enantiopure (T)-scrinc leads to a cyclic N,O-acetal functionality with the required functionality for the attachment of the side chain (Scheme 6) [36]. 

In contrast to ionized alkenols, which have been extensively investigated133, radical-cations derived from alkenylamines have received much less detailed attention. This omission, which partly reflects the relative difficulty in synthesizing unsaturated amines, particularly if incorporation of 2H- or 13C-labels is required, is unfortunate because the chemistry of ionized alkenols134 and the derived ionized ethers, which have been studied more recently135-138, is rich and interesting. 

The UV maximum (215 nm) of /l,y-unsaturated amine 25 (71JHC7) enables differentiating it from an isomeric enamine (a,)S-unsaturated... 

Application of the enamine-sulfene cycloaddition allowed the synthesis of 78 and 79 from the corresponding a,/l-unsaturated amines and sulfenes. Similarly, using enamine 80, the crystalline morpholino thietane dioxides (81) were produced. Elimination via the N-oxide gave the corresponding thiete dioxide, whereas reduction by LiAlH4 yielded the thietane 82. 

The radical pair generated by proton transfer from tertiary amine radical cations to a,p-unsaturated ketone radical anions (e.g., 71) couple in the p position, forming... 

The reaction of potassium dienoxy borates with A-fluorobis(phenylsulfonyl)amine (la) gives y-fluoro enones in good yield. The potassium dienoxy borates are prepared by treating potassium enolates derived from unsaturated ketones with 2-phenyl-1,3,2-benzodioxaborole. This methodology offers a convenient alternative to the traditional fluorination of dienol acetates, ethers, or enamines.145 An example is given by the formation of 13.145... 

Analogous to the use of chiral enoates (see previous section), a, -unsaturated carboxylic amides, prepared from chiral amines, may be utilized in asymmetric 1,4-additions. When Grignard reagents are added to unsaturated amides (21), derived from (-)-ephedrine (20),25 highly optically active fi-sub-stituted alkanoic acids (22 R and R = alkyl or phenyl) are obtained in a variety of cases, after hydrolysis of the initially formed adducts (Scheme 7). This method was used for the synthesis of the antibiotic (-) malyngolide and its stereoisomers.26 Recrystallization of the intermediate (saturated) amide was necess-... 

Fused ring products also may be formed from the transannular cyclization of medium ring unsaturated amine derivatives, as shown in Table 27.218 A transannular cyclization to the loline ring system was reported by Wilson (entry 4).218c Cyclization of a tertiary amine to a pyrrolizidine perchlorate has also been reported.219... 

Aziridinyl ketones can be synthesized from unsaturated carbonyls using a series of other methods. For example, azabicyclo[4.1.0]heptanone 27 was obtained from cyclohexenone 25 in its reaction with TV-bromotoluenesulfona-mide sodium salt 33 [49] (Scheme 1.10). The reaction of chalcone with N-chlorotoluenesulfonamide in the presence of silver nitrite is described in [50]. Trans-Aziridinyl ketone 18 was synthesized by reacting chalcone 22 with N,N-diamino-l,4-diazoniabicyclo[2.2.2.]octane dinitrate 34 and sodium hydride in 2-propanol [30, 51]. Aziridinyl ketones can be obtained in the reaction of a -unsaturated ketones with A,A-dichlorosulfonamines [52] and with amines in the presence of lead tetraacetate and trifluoroacetic acid [53] or in the presence of triethylammonium acetate under electrochemical reaction conditions [54]. 

Based on this concept, Whitby and co-workers [110] reported an interesting palladium-catalyzed three-component synthesis of aromatic and heteroaromatic amidines 133 starting from unsaturated halides, amines, and t-butylisocyanide (Scheme 8.53). The catalytic cycle for this iminocarbonylative coupling reaction is analogous to the reactions incorporating carbon monoxide-isoelectronic with isocyanides-as the third partner [111]. 

Silver hydroxide is used in exhaustive methylation, a process often utilised in order to obtain an unsaturated cyclic hydrocarbon from an amine by treating it with methyl iodide aud silver hydroxide the triniethyl-ammonium hydroxide obtained is then decomposed by distillation. 

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