ChemInform Abstract: Mild Arming and Derivatization of Natural Products via an In(OTf)₃‐Catalyzed Arene Iodination.

Abstract

Mild Arming and Derivatization of Natural Products via an In(OTf) 3 -Catalyzed Arene Iodination. -A variety of aromatic compounds is easily converted to the corresponding iodides using the mild reaction with NIS and In(OTf)3 as a catalyst. β-Estradiol (VIII) is easily iodinated and the functionalization of the product is demonstrated [cf. (XI), (XIII)]. Anti-inflammatory agent resveratrol (XIV) does not require any catalyst (to be continued). -(ZHOU, C.-Y.; LI, J.; PEDDIBHOTLA, S.; ROMO*, D.; Org. Lett. 12 (2010) 9, 2104-2107, DOI:10.1021/ol100587j ; Dep. Chem., Tex. A&M Univ., College Station, TX 77842, USA; Eng.) -R. Steudel

Diazo Reagents with Small Steric Footprints for Simultaneous Arming/SAR Studies of Alcohol-Containing Natural Products via O–H Insertion

“…We previously described mild and versatile strategies for simultaneous arming (with a reactive functional group or array) and SAR studies that facilitate mechanism of action studies of natural products. , One such method involves chemosite selective and site nonselective O–H insertions with rhodium carbenoids derived from hexynyl-α- p -bromophenyl diazo acetate ( 1 , HBPA) as a donor/acceptor carbenoid precursor . The arming process leads to natural product derivatives that are equipped with tethered alkynes for subsequent conjugation to various tags via Sharpless–Hüisgen cycloaddition to generate cellular probes.…”

A Green Alternative for the Direct Aerobic Iodination of Arenes Using Molecular Iodine and a POM@MOF Catalyst

“…2 Until now, several compounds have been used as starting materials to prepare iodoarenes including organotrifluoroborates, 3 alcohols, 4 aryl carboxylic acids, 5 arylboronic acids, 6 halogenated aromatics, 7 arylamines, 8 and arenes. 9 The arenes are very attractive as starting compounds, due to their low cost and high availability. The second ingredient, the iodinating compound, consists of one of two types: (i) iodides, such as N-iodosuccinimide, 1 iodobenzene diacetate, 10 and potassium iodide or (ii) simply molecular iodine.…”

Iodine(III)-Mediated, Controlled Di- or Monoiodination of Phenols

“…10 Due to the high relevance of the iodophenol moiety, several procedures have been developed to date for its synthesis. Among the most significant iodination strategies are those involving transition metals such as Ru, 11 In, 12 Pd, 13 Mo, 14 Hg, 15 Fe, 16 Ce, 17 Yb, 18 or Ag. 19 A number of transition-metalfree iodination procedures have also been described using I 2 in combination with 1,4-bis(triphenylphosphonium)-2-butene peroxodisulfate, 20 DMSO, 21 HIO 3 , 22 urea-H 2 O 2 , 23 or NO 2 .…”

“…C{ 1 H} NMR (126 MHz, CDCl 3 ) δ 162.74 (d, J = 247.0 Hz), 154.8, 136.7 (d, J = 3.3 Hz), 136.9, 134.8 (d, J = 3.1 Hz), 131.2 (d, J = 17.9 Hz), 130.1, 128.9 (d, J = 8.0 Hz), 127.7, 126.1, 117.1, 115.9 (d, J = 21.5 Hz), 86.4. HRMS (EI): m/z calculated for C 16 H 10 FIO [M] + = 363.9760, found 363.9753.6-(4-Chloro-3-fluorophenyl)-1-iodonaphthalen-2-ol(12). The following compound was obtained according to the general procedure A, by using 6-(4-chloro-3-fluorophenyl)naphthalen-2-ol as starting material and NH 4 I.…”