o-Benzenedisulfonimide: An Organic Reagent and Organocatalyst of Renewed Interest

Abstract

ABSTRACT:Synthesized nearly one century ago as a saccharine-like sweetener compound, the obenzenedisulfonimide has received a discontinuous attention in the past. In the last century, various synthetic procedures have been reported, in confirmation of the interest in this intriguing compound. In recent years, it has been used as a leaving group in reactions of nucleophilic substitution of amines with alcohols or phenols to give the corresponding ethers. Its Nfluoroderivative is a stable and efficient fluorinating agent, which has found applications in several asymmetric syntheses. In previous studies, its conjugated base has been extensively used as stabilizing counter-ion of arenediazonium salts; safely isolated and stored in a dry state, ready to use, they have been applied successfully in many dediazoniation reactions, with interesting mechanistic insights. More recently, due to its high acidity, the o-benzenedisulfonimide has been used in catalytic amounts in some common acid-catalyzed organic reactions. Valuable aspects of this catalyst are its easy recovery from the reaction mixture and its reuse in other reactions, with clear economic and ecological advantages. Finally, the disulfonimide functional group has been proposed as a powerful chiral motif for strong Brønsted acids in asymmetric organocatalysis.

New Potent Fluorescent Analogues of Strigolactones: Synthesis and Biological Activity in Parasitic Weed Germination and Fungal Branching

“…Coupling partners p-methoxyphenyl-(PMP), p-(dimethylamino)phenyl-(p-DMAP), 2-thienyl-, 6-methoxy-2-naphthyl-boronic acids (PMN) were used, and corresponding coupling products 18a-d were obtained in good yields. The corresponding triflates 19a-d were then generated in the presence of KHMDS and N-phenyltriflimide, and coupled with the ethoxy dienyl boronic ester 20 to afford compounds 21a-d which were then cyclized according to a Nazarov electrocyclic process catalyzed by o-benzenedisulfonimide, [34] and finally coupled with bromobutenolide 4 under the usual conditions. [31] The synthesis of derivative 28 required a different sequence of synthetic steps due to the acid lability of the 2,3-dihydrothieno [3,4-b] [1,4]dioxin moiety which was incapable of surviving Nazarov reaction conditions.…”

Strigolactones: Phytohormones with Promising Biomedical Applications

“…Suzuki coupling of 31 with alkoxy dienyl boronate 32 [22] allows the installation of the chain needed for the construction of ring C (see Figure 1). This was realized according to a Nazarov electrocyclic process catalyzed by o ‐benezendisulfonimide (o‐BDS) [23] . Suzuki coupling with 2‐(2,3‐dihydrothieno[3,4‐b][1,4]dioxin‐7‐yl)‐5,5‐dimethyl‐1,3,2‐dioxaborinane (not shown) and coupling with bromobutenolide 25 , [24] led to the final compound 20 b as a mixture of diastereoisomers which were isolated for bioactivity evaluation and further applications…”

“…This was realized according to a Nazarov electrocyclic process catalyzed by o-benezendisulfonimide (o-BDS). [23] Suzuki coupling with 2-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7yl)-5,5-dimethyl-1,3,2-dioxaborinane (not shown) and coupling with bromobutenolide 25, [24] led to the final compound 20 b as a mixture of diastereoisomers which were isolated for bioactivity evaluation and further applications 6) illustrate the differences in orientation of the BC ring junction which defines the two families strigol-like and orobanchol-like. In non-canonical SLs the ABC core is no longer in place as shown in 9-12 while the butenolide D-ring is present with the same R configuration at the 2' in the whole series of natural SLs.…”