Methyl 4-iodobenzoate

A complementary approach to six-membered rings can be achieved with methyl 2-iodobenzoate or 2-iodobenzoyl chloride, as shown in Scheme 16 (Grigg et al. 2002). 

The third-generation dendrimer palladium complex (31, containing 24 PdC groups) was applied in the Stille coupling of methyl-2-iodobenzoate with 2-(tributyl-stannyl)thiophene in DMF (Scheme 10 lmol% catalyst). In contrast to what was observed with the monomer (PPh3)2PdCl2, no palladium metal formation was... 

Several commercial products have been produced via Heck reactions on a scale in excess of one ton year"1 [43]. The sunscreen agent 2-ethylhexyl-p-methoxycinna-mate has been synthesized on a pilot scale by using Pd/C as the catalyst [44]. Albermarle produces Naproxen via a Heck reaction of 2-bromo-6-methoxy-naphthalene with ethylene, followed by carbonylation of the product [45]. A key step in the production of Singulair (montelukast sodium), a leukotriene receptor antagonist for treatment of asthma, is Heck reaction of methyl 2-iodobenzoate with an allylic alcohol to give a ketone [43]. 

The (E)- and (Z)-regioisomers of 6-ethylidenedioxadisilacyclohexane 1134 undergo palladium catalyzed-cross coupling with methyl-2-iodobenzoate to furnish dihydroisocoumarins with excellent (E)- or (Z)- selectivity (Scheme 282) <20030L1119>. 

A palladium-catalyzed three-component reaction with 2-iodobenzoyl chloride or methyl 2-iodobenzoate, allene and primary aliphatic or aromatic amines to prepare fV-substituted 4-methylene-3,4-dihydro-1 (27/)-isoquinolin-1 -ones was disclosed <02TL2601>. A synthesis of 1-substituted 1,2,3,4-tetrahydroisoquinolines via a Cp2TiMe2-catalyzed, intramolecular hydroamination/cyclization of aminoalkynes was also reported <02TL3715>. Additionally, a palladium-catalyzed one-atom ring expansion of methoxyl allenyl compounds 79 to prepare compounds 80 that can serve as precursors to isoquinolones was reported <02OL455,02SL480>. 

Copper(l) thiophene-2-carboxylate (CuTC, 5.70 g, 30 mmol, 3 eq.) was added in one portion to a solution of methyl 2-iodobenzoate (25, 2.62 g, 10 mmol) in A-methyl pyrrolidinone (30 ml, NMP) under a nitrogen atmosphere. After being stirred at room temperature for 1 h, the mixture was diluted with ethyl acetate (100 ml), and the resulting slurry was passed through a plug of silica gel using ethyl acetate as eluent (500 ml). Solvents were removed by evaporation and then vacuum distillation (NMP). 

In 2011, Bhanage and co-workers reported a carbon monoxide-free one-step synthesis of phthalimides by using formamides as an amine and CO source. With POCI3 as the activator, various phthalimides were produced in moderate to excellent yields (Scheme 2.2). In addition to 1,2-dihalobenzenes, 2-iodobenzoic acid and methyl 2-iodobenzoate can be applied as substrates for phthalimide preparation with formamides as an amine and CO source as well. This methodology was extended and applied in the synthesis of isobenzofuran-l(3/f)-one (70% yield) by using o-iodoben l alcohol as the substrate. 

Condensation of 2-methylquinolone 9 with dialdehyde 10 (1.5 mol equiv), in the presence of acetic anhydride afforded, after elimination of approximately 20% of Ws-adduct, compound 11 in 65% overall yield as a pure -isomer. Grignard reaction with vinylmagnesium bromide 12, under standard conditions, gives the expected scc-alcohol 13, which is condensed with methyl-2-iodobenzoate 14, in the presence of palladium acetate and lithium acetate in DMF, to yield ketone 15. 

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