Asymmetric α-Sulfonyl- and α-Phosphoryl-Oxylation of Ketones by a Chiral Hypervalent Iodine(III)

Abstract

An enantioselective direct oxygenation of propiophenone derivatives mediated by a catalytic or stoichiometric amount of new chiral non-C2-symmetric iodoarenes(III) is reported. The reaction gives an easy entry to optically active α-sulfonyl- and α-phosphoryl oxyketones in respectable yields and enantioselectivities.

Indanol‐Based Chiral Organoiodine Catalysts for Enantioselective Hydrative Dearomatization

“…[2][3][4][5] These chiral catalysts have already found application in av ariety of reactions,g iving enantioenriched products that are accessible only through the use of organoiodine catalysis. [6] However,chiral organoiodine catalysts that surpass the selectivity achievable with these leading catalysts is virtually non-existent, [7] and many organoiodine-catalyzed reactions are still performed with unsatisfactory levels of selectivity. [7,8] As as olution to overcome this limitation, we became interested in applying our chiral indanol scaffold, which has demonstrated outstanding selectivity in our studies on at hiyl radical and ae lectrophilic selenium catalyst, [9] to design anew chiral organoiodine catalyst ( Figure 1b).…”

“…[6] However,chiral organoiodine catalysts that surpass the selectivity achievable with these leading catalysts is virtually non-existent, [7] and many organoiodine-catalyzed reactions are still performed with unsatisfactory levels of selectivity. [7,8] As as olution to overcome this limitation, we became interested in applying our chiral indanol scaffold, which has demonstrated outstanding selectivity in our studies on at hiyl radical and ae lectrophilic selenium catalyst, [9] to design anew chiral organoiodine catalyst ( Figure 1b). [10] As aproof of concept, we surmised that enantiocontrol of the hydrative dearomatization of phenols at the para position, to give p-quinols would be particularly challenging and rewarding ( Figure 1c).…”

Indanol‐Based Chiral Organoiodine Catalysts for Enantioselective Hydrative Dearomatization

“…This organoiodine catalysis has recently attracted considerable attention in synthetic organic chemistry as away to implement oxidation reactions with low environmental impact. [6] However,chiral organoiodine catalysts that surpass the selectivity achievable with these leading catalysts is virtually non-existent, [7] and many organoiodine-catalyzed reactions are still performed with unsatisfactory levels of selectivity. [2][3][4][5] These chiral catalysts have already found application in av ariety of reactions,g iving enantioenriched products that are accessible only through the use of organoiodine catalysis.…”

“…[1] Thec urrent emphasis on this area has been driven by the emergence of effective chiral organoiodine catalysts,w hich has paved the way for highly enantioselective transformations (Figure 1a). [7,8] As as olution to overcome this limitation, we became interested in applying our chiral indanol scaffold, which has demonstrated outstanding selectivity in our studies on at hiyl radical and ae lectrophilic selenium catalyst, [9] to design anew chiral organoiodine catalyst (Figure 1b). [6] However,chiral organoiodine catalysts that surpass the selectivity achievable with these leading catalysts is virtually non-existent, [7] and many organoiodine-catalyzed reactions are still performed with unsatisfactory levels of selectivity.…”

C−O coupling of Malonyl Peroxides with Enol Ethers via [5+2] Cycloaddition: Non‐Rubottom Oxidation

“…In a number of studies direct hydroxylation of ketones [36] was achieved by using hypervalent iodine compounds, [37] molecular oxygen, [38] [39] DMSO/I 2 or DMSO/NBS, [40] DMSO/CuBr 2 or DMSO/HBr, [41] thallium(III)/p-nitrobenzenesulfonate, [42] Ti(O i Pr) 4 / TBHP [43] and PhNO/TFA. [44] In regard to the oxyfunctionalization of carbonyl targets, [45] they were previously limited to the alkoxy, [46] peroxy, [47] oxygensulfonyl, [48] oxygen-phosphoryl, [49] aminoxy [50] groups. In a few studies α-acyloxy-carbonyl products were synthesized using Cu/CuI/air, [51] Cu(acac) 2 /TBHP, [52] CuI/O 2 , [53] Pybox-Cu(II) complex/K 4 [Fe(CN) 6 ], [54] TBAI/H 2 O 2 [55] or TBAI/TBHP, [56] hypervalent iodine compounds, [57] N-methyl-O-benzoylhydroxylamine hydrochloride, [58] or TBAI/electric current.…”