Olefin diamination reactions

Scheme 5.15 Pd-catal3 ed diamination reaction of terminal olefins reported by Shi.

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... 

Selenium diimides react with unsaturated organic compounds. (tBuN)2Se is an in situ reagent for allylic amination of olefins and acetylenes. Improved procedures for the diamination of 1,3-dienes have been developed using (RN)2Se (R = /wu-toluenesulfonyl, ort/zo-nitrobenzenesulfonyl).156 The reaction of A iV -dialkyl selenium diimides with fe(amino)stannylenes produces four-membered SnNSeN ring systems.157... 

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. 

Episulfides, which can be generated in situ in various ways, react similarly to give p-amino thiols,835 and aziridines give 1,2-diamines.836 Triphenylphosphine similarly reacts with epoxides to give an intermediate that undergoes elimination to give olefins (see the Wittig reaction, 6-47). 

Primary (R = H) and secondary aromatic amines react with alkenes in the presence of thallium(III) acetate to give vic-diamines in good yields.806 The reaction is not successful for primary aliphatic amines. In another procedure, olefins can be diaminated by treatment with the osmium compounds R2N0s02 and R,NOsO (R = r-Bu),807 analogous to the osmium compound mentioned at 5-39. The palladium-promoted method of 5-39 has also been extended to diamination.808 Alkenes can also be diaminated800 indirectly by treatment of the aminomercurial compound mentioned in 5-39 with a primary or secondary aromatic amine.810... 

Olefins react directly at the electron-rich and rather electron-deficient oxygens. If the dimer is much more reactive toward olefins than the monomer, only a small fraction of the alkaloid-Os04 complex need be present as a dimer (94a). Houk developed a symmetrical five-membered transition-structure model on the basis of X-ray crystal structures of Os04-amine complexes and osmate ester products and ab initio transition structures of analogous reactions (Scheme 40). The MM2 calculations based on this [3 + 2] reaction model reproduce the stereoselectivities of the stoichiometric reactions observed with several chiral diamines (94b). The transition state may be stabilized by tt-tt interaction of the alkene substrate and the ligand aromatic ring (95). 

Nitrogen-transfer reactions of osmium imido species lead to cis diamines or amino alcohols. Reaction of 0s02(N-/-C4H9)2 [63174-13-0] with olefins produces vicinal diamines after reductive cleavage. Catalytic oxyamination of olefins using chloramine-T or AJ-chlor-AJ-argenocarbamates yields vicinal hydroxy toluenesulfonamides (112) or carbamates (113), respectively, which maybe deprotected to vicinal amino alcohols. 

Olefins - [FEEDSTOCKS - COALCHEMICALS] (Vol 10) - [FEEDSTOCKS-PETROCHEMICALS] (VollO) - [HYDROCARBONS - SURVEY] (Vol 13) -m automobile exhaust [EXHAUSTCONTROL, AUTOMOTIVE] (Vol 9) -catalyst for stereospeafic polymerization [TITANIUMCOMPOUNDS - INORGANIC] (Vol 24) -esters from [ESTERIFICATION] (Vol 9) -hydroxylation using H202 [HYDROGEN PEROXIDE] (Vol 13) -luminometer ratings [AVIATION AND OTHER GAS TURBINE FUELS] (Vol 3) -osmium oxidations of [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -polymerization [SULFONIC ACIDS] (Vol 23) -reaction with EDA [DIAMINES AND HIGHER AMINES ALIPHATIC] (Vol 8) -silver complexes of [SILVER COMPOUNDS] (Vol 22)... 

Consequently, new dilithium-nickel-olefin complexes with tetra- or pentacoordinated nickel atoms are formed, e.g., the Li2Ni complexes Li2Ni[(CH3)2NCH2CHCHCH2N(CH3)2]3 (18), (LiTMEDA)2Ni(C2H4)3 (19), (LiTMEDA NifCVHw (20), and (LiTHF)2Ni(C4H6)3 (21), by reaction with N,N,N, TV -tetramethy lbutene-2-diamine, ethylene, norbor-nene, or butadiene (14, 31-33). 

Those reactions in which N,N,N, N -tetramethylethylenediamine was added gave no formation of insoluble material. In addition, the rate of formation of the soluble polysulfides was increased as shown not only by the amount of these polysulfides formed but also by their molecular weight distributions (see below). With a 25% loading after 1 hr, reaction is incomplete, with unreacted olefin still present. But, if the diamine is used, all the olefin reacts after 1 hr, and the resultant material contains 31.5% soluble polysulfides. 

The hydroxy-binaphthyl functionalised saturated imidazolium salt is readily available from 1-amino-I -hydroxy-binaphthyl in a reaction with a ( oc-protected mesitylamine aldehyde [86] (see Figure 4.24). The resulting Schiff base is reduced to the diamine by Na(OAc)3BH. Subsequent deprotection and ring closure reaction with triethyl orthoformate yields the corresponding hydroxy-binaphthyl functionalised saturated imidazolium salt. Reaction with silver(I) carbonate and subsequent carbene transfer to the ruthenium(II) precursor yields the asymmetric olefin metathesis precatalyst. 

The reactions of iridium olefin complexes are not restricted to reactions with phosphines. Amines have also employed in bridge-splitting and substitution reactions with [Ir(COD)Cl]2, especially chelating diamines. The reactions proceed to yield [Ir(COD)N-N]2 compounds. A fertile chemical area involves the irw(pyrazolyl)borate (see Tris(pyrazolyl)borates) family of compounds with the monoethylene and bisethylene complexes serving as reactive entries in this field. ... 

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