Electrocatalytic addition of thiols to activated olefins

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 260–261, January, 1991.     

Double michael addition reactions to tetrakis sulfonyl activated olefins

A new class of bis Michael adducts are prepared from 1,3‐bis‐[2‐(2‐arylethenesulfonyl)‐vinyl]‐benzenes and 1,4‐bis‐[2‐(2‐arylethenesulfonyl)‐vinyl]‐benzenes by double Michael addition reaction with active methylene compounds.     

Michael addition of novel acyl anion equivalents generated by the electroreduction of oxazolinium salts to activated olefins

Electroreduction of oxazolinium salts gave novel acyl anion equivalents (AAEs), and the Michael addition of these AAEs to activated olefins has been found to be promoted effectively by the addition of chlorotrimethylsilane into the reaction system. This reaction was applied to the synthesis of cis-jasmone and dihydrojasmone.     

Studies on sulfinatodehalogenation: The addition of polyfluoroalkyl iodides to olefins promoted by sodium bisulfite and sodium sulfite

The reaction of polyfluoroalkyl iodides with alkenes or 4-pentenoic acid promoted by sodium bisulfite or sodium sulfite in DMF aqueous solution was realized. The reaction of alkenes gave corresponding adducts, while γ-lactones were obtained in the case of 4-pentenoic acid in good yields.     

Intermolecular cross-double-michael addition between nitro and carbonyl activated olefins as a new approach in C-C bond formation

A novel intermolecular cross-double-Michael addition between nitro and carbonyl activated olefins has been developed through Lewis base catalysis. The reaction took place with a large group of beta-alkyl nitroalkenes and alpha,beta-unsaturated ketone/esters, producing an allylic nitro compound in good to excellent yields.     

Addition of primaryN-nitroamides to activated olefins

PrimaryN-nitrosulfamides readily undergo addition to acrolein and vinyl ketones to yieldN--oxoalkyl-N-nitrosulfamides. The presence of a second substituent at the double bond hinders the reaction.N-Nitrourethane reacts with activated carbonyl compounds and -nitroolefins.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1261–1263, July, 1994.     

Palladium-catalyzed addition reaction of polyhaloalkanes to olefins

Pd(OAc)₂ combined with phosphines catalyzes homolytic cleavage of the C—Cl bond of CCl₄ and CCl₃CO₂CH₃ leading to facile addition to olefins under mild conditions. BrCCl₃ also reacts with olefins to give 1,1,1-trichloro-3-bromoalkanes. The reaction is accelerated under CO atmosphere, and the presence of bases such as NaOAc or K₂CO₃ is essential to attain high yields of the adducts.     

Rongalite-initiated addition of perfluoroalkyl iodides to olefins

Perfluoroalkyl iodides reacted with olefins in aqueous acetonitrile in the presence of Rongalite-sodium bicarbonate under mild conditions to give the corresponding 1:1 adducts in moderate to high yields. The formation of these products and the orientation of the addition seemed to show that radicals took part in the reaction. This provides a convenient method for perfluoroalkylation.     

“Selenosulfonation”: the addition of selenolsulfonates to olefins

The reaction of phenyl areneselenolsulfonates with unhindered olefins affords β-phenylselenosulfone adducts, usually with high regio- and stereoselectivity.     

Concise synthesis of novel practical sulfamide-amine alcohols for the enantioselective addition of diethylzinc to aldehydes

Novel sulfamide-amine alcohol ligands were designed using a grafting strategy and synthesized from readily available starting materials via a simple, efficient method. The key features of these ligands for the asymmetric addition of diethylzinc to aldehydes included stability, enhanced effectiveness without using Ti(O(i)Pr)(4), suitability for a variety of aldehydes, the ability to operate at room temperature, and selectability to afford either absolute configuration products with enantiomeric excess up to >99%.     

The electrophilic addition of selenenyl thiocyanates to olefins

Benzeneselenenyl thiocyanate in methanol reacts with olefins to give adducts; kinetic data for attack upon styrenes are presented.     

Highly regio- and chemoselective palladium-catalyzed propargylallylation of activated olefins: a novel route to 1,7-enyne derivatives

An efficient method for the synthesis of 1,7-enyne derivatives via phosphine-palladium-catalyzed three-component assembling of activated olefins, allylic chlorides, and allenylstannanes is described. Substituted arylethylidene malononitriles 1a-g (RCH=C(CN)(2): R = C(6)H(5) (1a), p-ClC(6)H(4) (1b), p-OMeC(6)H(4) (1c), p-NO(2)C(6)H(4) (1d), 1-naphthyl (1e), 2-furyl (1f), and 2-thienyl (1g)) undergo propargylallylation with allylic chlorides 2a-e (allyl chloride (2a), methallyl chloride (2b), 4-chloropent-2-ene (2c), cinnamyl chloride (2d), and 3-chlorocyclohexene (2e)) and n-tributylallenylstannane (n-Bu(3)SnCH=C=CH(2), 3a) in the presence of Pd(PPh(3))(4) in toluene to afford the corresponding 1,7-enyne derivatives 4a-m in good to excellent yields. The catalytic reaction is highly regioselective, with the propargyl group adding to the carbon where the R group is attached and the allyl group adding to the carbon connected to the CN groups of activated olefins 1a-g. The present catalytic reaction is successfully extended to substituted arylethylidene-1,3-indanediones 5a-j (RCH = (1,3-indanedione): R = C(6)H(5) (5a), p-ClC(6)H(4) (5b), p-BrC(6)H(4) (5c), p-OMeC(6)H(4) (5d), p-NO(2)C(6)H(4) (5e), p-CNC(6)H(4) (5f), p-biphenyl (5g), 1-naphthyl (5h), 2-thienyl (5i), and 2-benzo[b]furane-2-yl (5j)) and substituted 2,2-dimethyl-5-(arylethylidene)-1,3-dioxane-4,6-diones 7a,b (RCH = (1,3-dioxane-4,6-dione): R = p-NO(2)C(6)H(4) (7a), p-OMeC(6)H(4) (7b)). The three-component assembling of these substrates with allylic chlorides (2a,b,d,e) and n-tributylallenylstannane (n-Bu(3)SnCH=C=CH(2), 3a) proceeds smoothly to afford the corresponding 1,7-enyne derivatives 6a-m and 8a-d in good to excellent yields. The catalytic propargylallylation can be further applied to the activated dienes, C(6)H(5)CH=CH=CR(2) (R(2) = (CN)(2) (9a), 1,3-indanedione (9b), 2,2-dimethyl-1,3-dioxane-4,6-dione (9c)), with allylic chlorides (2a,b,d) and allenylstannane 3a to give regio- and chemoselective 1,2-addition products 10a-h in good to excellent yields. A plausible mechanism based on an eta(1)-allenyl eta(3)-allyl palladium intermediate is proposed to account for the catalytic three-component reaction.     

Rare-earth-catalyzed C-H bond addition of pyridines to olefins

An efficient and general protocol for the ortho-alkylation of pyridines via C-H addition to olefins has been developed, using cationic half-sandwich rare-earth catalysts, which provides an atom-economical method for the synthesis of alkylated pyridine derivatives. A wide range of pyridine and olefin substrates including α-olefins, styrenes, and conjugated dienes are compatible with the catalysts.     

Molecular mechanism of hydrogen bromide addition to olefins

Experimental results on the products and the kinetics of the hydrogen bromide addition to alkenes-1 in non-polar solvents and on complex formation in hydrogen bromide-olefin-solvent systems are reviewed. Theoretical calculations concerning hydrogen bromide-olefin complexes are used along with the experimental evidence to suggest a molecular mechanism of addition involving intermediate cyclic structures.     

An unprecedented tandem 1,3-dipolar cycloaddition-cheletropic elimination: a facial approach to novel push-pull olefins

The interaction of 2-(phenylthiocarbamoyl) imidazolium inner salts with dimethyl acetylenedicarboxylate produced dimethyl 2-(imidazolin-2-ylidene)-3-thioxobutanedioates in moderate to good yields. The process involved a tandem reaction comprising a 1,3-dipolar cycloaddition and an unprecedented cheletropic elimination of the phenyl isonitrile from a 2-phenyliminodihydrothiophene moiety. NMR and X-ray diffraction studies confirmed that the 2-(imidazolin-2-ylidene)-3-thioxobutanedioates are novel push-pull olefins and have potential applications in nonlinear optical materials.