Unsymmetrical Ketone Synthesis via a Three-Component Connection Reaction of Organozincs, Allylating Agents, and Carbon Monoxide

Stereoselective Synthesis of Trisubstituted Alkenes through Sequential Iron‐Catalyzed Reductive anti‐Carbozincation of Terminal Alkynes and Base‐Metal‐Catalyzed Negishi Cross‐Coupling

“…However, the lowering of the loading of bipy or CuI led to the decrease of yields (Table S1, entries 10 and 11). Other Cu catalysts were also screened but they did not catalyze the reactions as efficiently as CuI (Table S1, entries [12][13][14][15][16][17][18]. The use of other Zn activating reagents, bromo-and chlorotrimethylsilane (TMSBr and TMSCl), did not lead to a higher yielder yield compared to TMSI (Table S1, entries 19 and 20).…”

“…By using a higher loading of alkenylzinc reagent (1.7 equiv), the use of CoBr 2 /TMEDA/pyridine catalyst system could led to a highest yield of product in 76% yield (Table S3, entry 12). The subsequent tuning of loading of either TMEDA or pyridine did not promote the yield further (Table S3, entries [13][14][15]. Additionally, the conditions in entry 12 also allowed for the coupling of primary alkyl iodide, 1-iodooctane (test substrate, 0.10 mmol), to give the desired product in 76% yield Table S3, entry 12).…”

Cohalogenation of limonene, carvomenthene and related unsaturated monoterpenic alcohols

“…The reaction of (5R)-carveols 7 (1:1 mixture of cis 7a and trans 7b isomers by HRGC) with I 2 /H 2 O/Cu(OAc) 2 ·H 2 O for 5 h led to an iodopinol derivative (8) 22 and an iodohydrin (9) 23 , as shown in Scheme 5.…”

A New Sequential Intramolecular Cyclization Based on the Boekelheide Rearrangement

“…Route A involved a Pd II -catalyzed crosscoupling [21] between 2-bromopyridine and the required iodoalkanenitrile 13c,e (obtained from the commercially available chloroalkyl cyanide by chlorine/iodine exchange [20] ) to give the intermediates 14c,e, which -after reduction of the nitrile functionality, protection with Boc anhydride, and substitution with benzyl bromide -led to the [(benzylamino)alkyl]pyridines 20c,e. Route B consited of a Sonogashira coupling [22] of 2-or 4-bromopyridine with the commercially available alkynol 17 to give the intermediates 18a,b,d, which -by oxidation, reductive amination with benzylamine, and Boc protection -led to 20a,b,d.…”

“…Synthesis of 5-(1-Oxido-2-pyridinyl)-N-(phenylmethyl)-1-pentanamine (22c): Scheme 5, route A. 5-Iodopentanenitrile (13c), necessary for this synthesis, was prepared according to a literature procedure: [20] 5-Chloropentanenitrile (1.34 mL, 13.52 mmol) and NaI (6.08 g, 40.55 mmol) were stirred and refluxed in acetone (130 mL) under N 2 for 2 d. After distilling off the solvent, the residue was diluted with water and extracted with ethyl acetate (200 mL + 100 mL). The organic extracts were successively washed with 1 m Na 2 S 2 O 3 and saturated NaHCO 3 , dried (Na 2 SO 4 ), concentrated, and distilled under reduced pressure to give 6-iodopentanenitrile (13c) (2.60 g, 99 %) as a colourless liquid.…”