Hypervalent iodine compounds derived from o-nitroiodobenzene and related compounds: syntheses and structures

Abstract

A series of compounds possessing polyvalent iodine groups was prepared from onitroiodobenzene. Single crystal X-ray investigation revealed a strong interaction between iodine atom and one of the oxygen atoms of the nitro group. This interaction is strongest in trifluoroacetate of hydroxy(o-nitrophenyl)iodonium salt, which is formed from an iodosylarene and an acid being the first example of this new class of compounds. These compounds are also characterized by NMR-spectroscopy.

A new hypervalent iodine(iii/v) oxidant and its application to the synthesis of 2H-azirines

“…In general, the geometry of the trivalent I(1) center is consistent with that of the reported o -nitrophenylhydroxyiodonium molecule, with a strong interaction formed between the iodine atom and one of the oxygen atoms from the nitro group on the ortho -position of the phenyl ring. 29 In molecule 1 , the distance between I(1) and O(2) in the nitro group (2.638 Å) is slightly longer than that in the o -nitrophenylhydroxyiodonium molecule (2.510 Å), but is much shorter than the sum of the respective vdW radii (3.530 Å), indicating a strong interaction between the iodine atom and nitro group. 29 Similar to the attractive interaction between I(2) and O(6), I(1) and O(2) interaction was also found with the presence of a bond path and a BCP(2) ( Fig.…”

“…3B ), which was revealed previously. 29 In addition, DFT calculations were performed with ORCA 4.1.2 software. 30 The comparison of ρ bcp and the Mayer bond order of I 2 –O 3 bonds in the hypervalent iodine molecule with or without nitro groups was summarized, which showed that the I 2 –O 3 bond became weaker when the nitro groups in molecule 1 were deleted (see ESI, Fig.…”

CO2-activated NaClO-5H2O enabled smooth oxygen transfer to iodoarene: a highly practical synthesis of iodosylarene

“…In contrast to 4b, 2-(nitro)iodobenzene 4i selectively afforded pentavalent 2-nitro(iodyl)benzene (6b), probably due to the coordination of neighboring oxygen of the nitro group, which facilitates further oxidation. 19 It should be emphasized that the readily hydrolyzable 4-(methoxycarbonyl)iodosylbenzene 1d was selectively obtained in good yield under conventional hydrolysis conditions (Figure 1(A)) without saponification. 20 The attempted oxidation of highly electron-deficient pentafluoroiodobenzene (4j) was unsuccessful, in marked contrast to the facile oxidation of 4j in AcOH, yielding C6F5I(OAc)2.…”

“…17 1 H NMR (500 MHz, DMSO-d6): δ 8.37 (dd, J = 7.9, 1.2 Hz, 1H), 8.30 (dd, J = 7.9, 1.2 Hz, 1H), 8.19 (ddd, J = 7.9, 7.6, 1.2 Hz), 7.89 (ddd, 7.9, 7.6, 1.2 Hz). 19 Large-scale synthesis of 1a. To a stirred suspension of NaClO-5H2O (13.3 g, 80.8 mmol) in MeCN (40 mL) was added iodobenzene (4a) (15.0 g, 74 mmol) under CO2 at room temperature, and the mixture was vigorously stirred for 10 minutes.…”

“…. 43 Mp 117-118 °C; 1 H NMR (500 MHz, CDCl3): δ 7.84 (d, J = 8.4 Hz, 2H), 7.72-7.60 (m, 3H), 3.02 (s, 3H); 19 F NMR (470 MHz, CDCl3): δ -78.9 ppm (s, 3F).…”