Unsaturated Nitriles:  A Domino Ozonolysis−Aldol Synthesis of Highly Reactive Oxonitriles

Tandem Application of C–C Bond-Forming Reactions with Reductive Ozonolysis

“…26 Cyclic oxonitriles have been prepared by pairing the ozonolysis of unsaturated nitriles with a subsequent intramolecular aldol reaction. 27 Ozonides are also known to react directly with organometallic reagents. 28 However, this methodology requires handling of a peroxide intermediate and the use of excess organometallic (to cleave the O-O bond and then react with the liberated carbonyl).…”

Direct Assembly of Polysubstituted Naphthalenes via a Tandem Reaction of Benzynes and α-Cyano-β-methylenones

“…Benzyne precursors were obtained from commercial suppliers and used without purification. Benzyne precursors 2b , 2c ,α-cyano-β-methylenones 1a – 1x , 1y-1z, 1aa , 4a , 4b , 4c , and 4d were prepared according to literature procedures. Anhydrous THF, 1,4-dioxane, toluene, and DME were distilled from sodium and benzophenone prior to use.…”

“…Benzyne precursors were obtained from commercial suppliers and used without purification. Benzyne precursors 2b, 19 2c, 19 α-cyano-βmethylenones 1a−1x, 16 1y-1z, 20 1aa, 21 Typical Procedure for the Tandem Reaction of Benzyne and α-Cyano-β-methylenone. To a mixture of α-cyano-βmethylenone 1a (0.10 mmol, 24.7 mg) and TBAT (0.60 mmol, 323.9 mg) in anhydrous acetonitrile (1.0 mL) was added 2-(trimethylsilyl) aryl triflate 2a (0.20 mmol, 60.0 mg) under a nitrogen atmosphere.…”

Transformations of peroxide products of olefins ozonolysis

“…A synthesis was developed of six-membered (105) and seven-membered (106) oxocarbonitriles by successive zonolysis-reduction with Me 2 S and aldol condensation [42,43] The ozonolysis of hex-3-enedinitrile 107 and but-3-enenitrile 108 in the mixture of methanol and dichloromethane at -40°C with subsequent reduction of the peroxide ozonolysis products with dimethyl sulfi de afforded 3-oxopropanenitrile 109, transforming in some time into the corresponding acetal 110 [44] (Scheme 16).…”