An Investigation into the One-Pot Heck Olefination−Hydrogenation Reaction

Abstract

Herein is described an operationally simple process concerning the observation that, following either inter-, or intramolecular Heck olefination, stirring of the so formed substituted alkenyl product under an atmosphere of hydrogen efficiently effects alkene hydrogenation. Overall this two-operation, one-pot "reductive Heck" sequence is notable since direct reductive Heck processes, using additives such as formate salts, are restricted to a limited range of substrates. In total 25 examples are reported (yields ranging from 0 to 95%), which were selected in order to probe the scope and limitations of this method. Finally, the utility of this sequence was demonstrated in a short synthesis of the calcimimetic agent, cinacalcet.

Esterification, transesterification and hydrogenation reactions of polyunsaturated compounds catalyzed by a recyclable polymer supported palladium catalyst

“…The filtrate was evaporated under vacuum to give methyl 3-phenylpropionate as a pale yellow oil (763.5 mg, yield = 93 %). Comparison of its MS and NMR features with those reported in literature [37] confirmed the purity of the obtained product. …”

Visible-Light-Mediated Alkenylation, Allylation, and Cyanation of Potassium Alkyltrifluoroborates with Organic Photoredox Catalysts

“…Alkenyl sulfones were readily synthesized by several methods, including iodosulfonation–dehydroiodination of styrene derivatives, 10 olefination of α-sulfonylphosphonates, 11 or Heck reaction of phenyl vinyl sulfone with aryl halides. 12 The reaction conditions developed allowed a wide range of aryl subunits to be incorporated, including electron-deficient ( 3c – f ) and electron-rich arenes ( 3g and 3h ), providing the desired alkenyl pyrrolidines in acceptable yields (Table 1). Halide substitution, including that in fluoride 3i and bromides 3j and 3k , withstood the reaction conditions and may serve as handles for further diversification.…”

Synthesis of Amines from Alcohols in a Nonepimerizing One‐Pot Sequence – Synthesis of Bioactive Compounds: Cinacalcet and Dexoxadrol

“…To demonstrate the utility of this one-pot sequence, this method was applied to the synthesis of cinacalcet, [43][44][45][46][47] a clinically used calcimimetic agent (e.g., Sensipar, Mimpara). The synthesis would feature the N-alkylation of (R)naphthylethylamine [(R)-2b] with alcohol 4 (see Scheme 4).…”

“…in ethanol (50 mL). [43] General Procedure to Access Primary Amines: 2,2,6,6-Tetramethyl-1-piperidinyloxyl (30 mg, 0.2 mmol, 0.2 equiv.) under 1 atm of H 2 , the reaction mixture was filtered through Celite and concentrated under reduced pressure.…”