Olefins oxyamination

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. 

Procedure A does not succeed with diethyl fumarate and 2-cyclohexen-1-one. Both chloramine-T and part of the olefin are consumed, but the oxyamination product has not been detected in the reaction mixtures. It seems likely that it forms, but is unstable to the reaction conditions. Both of these olefins do form isolable oxyamination products under the milder conditions (room temperature) of a more recent oxyamination procedure.5... 

OSMIUM-CATALYZED VICINAL OXYAMINATION OF OLEFINS BY CHLORAMINE-T cis-2-(p-TOLUENESULFONAMIDO)CYCLOHEXANOL AND 2-METHYL-3-(p-TOLUENESULFONAMIDO)-2-PENTANOL... 

Procedure A is very effective for most monosubstituted and 1,2-di-substituted olefins. This method,2 using phase-transfer conditions (PTC), has been developed recently in our laboratory and represents a substantial improvement over our former procedures.4 Cyclooctene, (Z)-5-decene, stilbene, ethyl crotonate, and 1-decene are among the olefins that are readily oxyaminated under the conditions described in procedure A. 

The PTC method gives poor results with trisubstituted and 1,1-disub-stituted olefins. The oxyamination product may still form, but it is accompanied by a number of by-products. Fortunately, this class of olefins is successfully oxyaminated by the alternative procedure (B). Methyl-cyclohexene, a-methylstyrene, 2-methyl-2-hepten-6-one, and its ketal are examples of olqfins that give oxyamination products in good yield following procedure B. 

OSMIUM-CATALYZED VICINAL OXYAMINATION OF OLEFINS BY JV-CHLORO-A-ARGENTOCARBAMATES ETHYL threo-l 1 (2-HYDROX Y-l, 2-DIPHENYI,-ETHYL)]CARBAMATE... 

OSMIUM-CATALYZED VICINAL OXYAMINATION OF OLEFINS BY Af-CHLORO-jV-ARGENTOCARBAMATES ETHYL fArco-[l-(2.HYDROXY-l,2-DIPHENYL-ETHYDICARBAMATE... 

An interesting offshoot of the work on osmium-catalyzed dihydroxylations is vicinal hydroxyamination [24]. Here, imido analogs of OSO4 react with olefins to produce /5-aminoalcohols by a cw-addition process. The oxyamination reaction can be made catalytic in OSO4 by employing chloramine salts of arylsulfonamides (ArS02NClNa) or carbamates. 

Sharpless and coworkers have reported a new series of reagents for allylic amination of olefins,79-5 vicinal oxyamination of olefins,76 and 1,2-diamination of 1,3-dienes.77... 

Oxyamination of olefins. This reagent reacts with a variety of olefins to give, after reductive cleavage of intermediate osmate esters, cis-vicinal amino alcohols in fair to high yield. The reaction is regiospecific in that the new C—N bond is formed at the least substituted carbon atom of the olefin. The reagent reacts more rapidly with monosubstituted olefins than with di- and trisubstituted olefins. Diols are obtained as the main products from hindered olefins. Methylene chloride or THF can be used as solvents, but pyridine is the solvent of choice. 

Oxyanunation. Vicinal oxyamination of olefins can be carried out with OSO4 in catalytic amounts with this N-chloro-N-argentocarbamate (c/. Osmium tetroxide-Chloramine-T, 7, 256). A major improvement over chloroamine-T is that the —COOCfCHaja group is readily eliminated. 

Oxyamination of olefinic sugars using the Sharpless reaction (TSNHCI-OSO4) has been widely studied as a route to amino-sugars. Compounds of the general... 

Improved procedures for osmium-catalysed vicinal oxyamination of olefins by JV-chlorosodiocarbamates-Hg(N03)2-Et4NOAc are recommended especially for trisubstituted systems. Asymmetric induction in the reaction of OSO4 with olefins using dihydroquinidine acetate in up to 83% e.e. is now possible. "... 

The palladium-catalysed oxyamination of olefins is well known, and it has now been found that, by the use of chiral reagents, asymmetry can be induced in the amination step and that optically active tertiary amino-alcohols result. 1-Piperidino-l-trimethylsilyloxycyclopropane and the corresponding 1-hydroxy-compound have been prepared and examined for their utility as cyclopropanone equivalents. ... 

Oxyamination. Efficient oxyamination of styrene derivatives was described using copper(II) trifluoroacetate as the catalyst. The corresponding aminals were obtained in moderate to good yields (eq 3). The oxyamination was regioselective and was performed with various styrenes and electron-rich olefins. 

Following the report last year of the first vicinal oxyamination of olefins using aminated derivatives of osmium tetroxide. Sharpless has extended this analogy to oxidations involving selenium dioxide. Two aza analogues of selenium dioxide have been prepared by either the reaction of selenium tetrachloride with the amine or... 

A new procedure for the v/c-oxyamination of olefins utilizes the trihydrate of chloramine-T and osmium tetroxide as a catalyst (Scheme 7). 

Waser J, Nambu H, Carreira EM (2005) Cobalt-catalyzed hydroazidation of olefins convenient access to alkyl azides. J Am Chem Soc 127(23) 8294-8295 Shyam PK, Jang HY (2014) Metal-organocatalytic tandem azide addition/oxyamination of aldehydes for the enantioselective synthesis of P-amino a-hydtoxy esters. Eur J Org Chem... 

Nocquet-Thibault S, Rayar A, Retailleau P, Cariou K, Dodd RH (2015) Iodine(in)-mediated diazidation and azido-oxyamination of enamides. (Them Eur J 21(40) 14205-14210 Yuan YA, Lu DF, Chen YR, Xu H (2016) Iron-catalyzed direct diazidation for a broad range of olefins. Angew Chem Int Ed 55(2) 534-538... 

Diphenyl sulphide reacts with anhydrous chloramine-T to give an adduct (8), which is a useful reagent for the amination of olefins (Scheme 7). The osmium-catalysed oxyamination of olefins by chloramine-T has been improved by phase-transfer catalysis, and the stereospecific vicinal oxyamination of olefins by alkylimido-osmium compounds has been reported. ... 

Improvements in the osmium-catalysed hydroxylation and oxyamination of olefins continue to appear." In the vicinal hydroxylation of olefins by t-butyl hydroperoxide earlier methods involved rather alkaline conditions, but this drawback has been overcome by using Et4NOAc instead of Et4NOH and changing the solvent from t-butyl alcohol to acetone."" Although the new method works well for base-sensitive compounds (e.g. esters), it fails with tetrasubstituted olefins. Yields are generally around 70%. Vicinal hydroxy-toluene-p-sulphonamides (8),... 

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