Alkene diamination

Primary (R = H) and secondary aromatic amines react with alkenes in the presence of thallium(III) acetate to give vie- diamines in good yields. " The reaction is not successful for primary aliphatic amines. In another procedure, alkenes can be diaminated by treatment with the osmium compounds R2NOSO2 and R3NOSO (R = t-Bu)," analogous to the osmium compound mentioned at 15-51. The palladium-promoted method of 15-51 has also been extended to diamination. " Alkenes can also be diaminated indirectly by treatment of the aminomercurial compound mentioned in 15-51 with a primary or secondary aromatic amine. 

The five-coordinate acyl complex may not be mononuclear. Using a rhodium complex in presence of a diamine, alkenes were converted to alcohols according to reaction (84),... 

The next method Strike has for semi-direct amination is really weird, Strike is really exposing Strike s ignorance of chemistry with this dog. But if one looks hard at the articles cited, the potential is there. The authors came up with this little procedure that produced vicinal diamines out of alkenes [83]. Later they found that if they did a couple of things different, they would end up with a monoamine with the majority product being at the beta carbon. The following is a conjoining of the two paper s experimentals ... 

Episulfides, which can be generated in situ in various ways, react similarly to give P-amino thiols, and aziridines give 1,2-diamines. Triphenylphosphine similarly reacts with epoxides to give an intermediate that undergoes elimination to give alkenes (see the Wittig reaction, 16-47). 

The [(T -C3H5)PdCl]2/dppf/AcOH catalytic system has been used for the bis(hy-droamination) of 3-alken-l-ynes to alkenic 1,4-diamines (Eq. 4.94), a reaction which seems to be mechanistically related to the hydroamination of allenes since an a-al-lenic amine CH2=C=CH(R )CH2NR2 is believed to be an intermediate [318]. 

Several catalysts that can effect enantioselective epoxidation of unfunctionalized alkenes have been developed, most notably manganese complexes of diimines derived from salicylaldehyde and chiral diamines (salens).62... 

The reactions of olefins with non-organometallic Tc(VII) compounds behaved similarly. In a recent study, [Tc03C1(AaA)] (86a) (in which AA stands for aromatic diamine derivatives) was shown to react quantitatively with olefins, and produce the corresponding Tc(V) diolato-complex [TcOC1(OaO)(AaA)] (87a). The process could not be run catalytically, as Tc(V) complexes tend to undergo disproportionation rather than reoxidation in the presence of water [97]. These alkene-glycol interconversions could not be performed with the analog Re(VII) compound. Rhenium displays completely contrary behaviour, in that alkenes can... 

A detailed study of the role of the base in the formation of 2-isoxazolines by condensation of primary nitro compounds with alkenes in the presence of the tertiary diamine 1,4-diazabicyclo[2.2.2]octane (DABCO) was published <06EJO4852 06EJ03016>. 

A Cu(OAc)2-catalyzed intramolecular diamination of alkenes using sulfamide substrates such as compound 214 provides a route to fused thiadiazolidines 215 (Equation 48) <2005JA11250>. In this reaction, the transition metal activates the alkene toward nucleophilic attack by the first nitrogen, then becomes displaced by the second nitrogen nucleophile (a net M +z to M reduction). 

In combination with the use of tetrasulfur tetranitride, trithiazyl trichloride, or any equivalent source of N-S-N , the technique of functionalizing a two-carbon source such as active methylene, alkene, or alkyne into thiadiazole (see Section 5.09.9.1.4) followed by reduction (see Section 5.09.5.6) provides a rapid route to 1,2-diamines. 

RuCl2(PPh3)3 has been shown to catalyze the reduction of several aldehydes, but does not have widespread scope. This catalyst is not chemoselective and, in the presence of alkenes, would favor olefin reduction over that of the aldehyde. Noyori and coworkers showed that chemoselectivity is easily introduced by the addition of ethylene-diamine as a ligand (Scheme 15.6) [29, 30]. This system requires the presence of co-catalytic KOH/i-PrOH as an activator. 

Brunner, Leitner and others have reported the enantioselective transfer hydrogenation of alpha-, beta-unsaturated alkenes of the acrylate type [50]. The catalysts are usually rhodium phosphine-based and the reductant is formic acid or salts. The rates of reduction of alkenes using rhodium and iridium diamine complexes is modest [87]. An example of this reaction is shown in Figure 35.8. Williams has shown the transfer hydrogenation of alkenes such as indene and styrene using IPA [88]. 

Since Sharpless discovery of asymmetric dihydroxylation reactions of al-kenes mediated by osmium tetroxide-cinchona alkaloid complexes, continuous efforts have been made to improve the reaction. It has been accepted that the tighter binding of the ligand with osmium tetroxide will result in better stability for the complex and improved ee in the products, and a number of chiral auxiliaries have been examined in this effort. Table 4 11 (below) lists the chiral auxiliaries thus far used in asymmetric dihydroxylation of alkenes. In most cases, diamine auxiliaries provide moderate to good results (up to 90% ee). 

In summary, the reaction of osmium tetroxide with alkenes is a reliable and selective transformation. Chiral diamines and cinchona alkakoid are most frequently used as chiral auxiliaries. Complexes derived from osmium tetroxide with diamines do not undergo catalytic turnover, whereas dihydroquinidine and dihydroquinine derivatives have been found to be very effective catalysts for the oxidation of a variety of alkenes. OsC>4 can be used catalytically in the presence of a secondary oxygen donor (e.g., H202, TBHP, A -methylmorpholine-/V-oxide, sodium periodate, 02, sodium hypochlorite, potassium ferricyanide). Furthermore, a remarkable rate enhancement occurs with the addition of a nucleophilic ligand such as pyridine or a tertiary amine. Table 4-11 lists the preferred chiral ligands for the dihydroxylation of a variety of olefins.61 Table 4-12 lists the recommended ligands for each class of olefins. 

Versions of these aminocyclopropanations of terminal alkenes can also be applied intramolecularly. Terminally ethenyl-substituted N,N-dialkylcarboxamides such as 67 yield l-(dialkylamino)bicyclo[n.l.O]alkanes such as 68, while (w-alkenylamino)carboxa-mides such as 69 and 71 lead to 1 -alkyl-2-azabicyclo u.l.0]alkanes such as 70 and 72 (Scheme 11.20) [86,118], and N-allylamino acid N,N-dialkylamides furnish bicyclic diamines (see below). 

Enantioselective osmylotion of alkenes. Osmium tetroxide forms a 1 1 wine-red complex with the chiral diamine l2 that effects efficient enantioselective dihy-droxylation of monosubstituted, oww-disubstituted, and trisubstituted alkenes (83-99% ee) at -110° in THF. The enantioface differentiation in all cases corresponds to that observed with t/mr-3-hexene and the complex with (-)-l. Essentially complete asymmetric induction is observed with frans-l-phenylpropene (99% ee). 

In a similar manner, polymers with unsaturated chains or side chains can be converted to polyamines [66-69]. Conjugated diolefins usually undergo hydroformylation with low selectivities [70]. Mostly hydrogenation of at least one double bond occurs and mixtures of various saturated and unsaturated amines and diamines are obtained [71]. Similar to alkenes also alkynes may serve as unsaturated compounds in hydro aminomethylation reaction sequences. Although synthetically attractive, only a few investigations towards hydroformylation and hydroaminomethylation of alkynes in the presence of N-nuclcophilcs are known. Usually a preferred transformation to furanonic derivatives is observed under hydroformylation conditions [27]. 

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