The synthesis of chiral β-naphthyl-β-sulfanyl ketones via enantioselective sulfa-Michael reaction in the presence of a bifunctional cinchona/sulfonamide organocatalyst

Abstract

Cinchona alkaloid-derived organocatalysts are widely employed in various asymmetric transformations, yielding products with high enantiopurity. In this respect, a bifunctional quinine-derived sulfonamide organocatalyst was developed to catalyze the asymmetric sulfa-Michael reaction of naphthalene-1-thiol with trans-chalcone derivatives. The target sulfa-Michael adducts were obtained with up to 96% ee under mild conditions and with a low (1 mol %) catalyst loading. Selected enantiomerically enriched sulfa-Michael addition products were subjected to oxidation to obtain the corresponding sulfones.

Bifunctional Sulfonamide as Hydrogen Bonding Catalyst in Catalytic Asymmetric Reactions: Concept and Application in the Past Decade

“…Moreover, this method could easily afford enantiopure β ‐functionalize cysteine in high ee value and dr ratio. The obtained cysteine derivates could be well applied in native chemical ligation studies In Tanyeli's work reported recently, treatment of thiols and trans ‐chalcone in the existence of quinine‐based sulfonamide 31 provided β ‐naphthyl‐ β ‐sulfanyl ketone products in extremely high yields (up to >99 %) and ee values (up to 96 % ee), which had potent anti‐breast cancer activity [57] . In addition, Enantioenriched sulfones, which had stronger bioactivity, could be easily accessed via the oxidation of β ‐sulfanyl ketones.…”

“…Hiemstra's group and Tanyeli's group were designed the cinchona alkaloid derived sulfonamide catalysts for catalyzing sulfa-Michael process of α,β-unsaturated ketones with thiols (Scheme 20). [56,57] In Hiemstra's work, cinchona alkaloid catalyst 30 with special sulfonamide moiety at C 6 ' position was synthesized to promote sulfa-Michael reaction in excellent yields (up to 99 %) and enantioselectivities (up to 99 % ee) with good diastereoselectivities (up to 93 : 7 dr). [56] Moreover, this method could easily afford enantiopure β-functionalize cysteine in high ee value and dr ratio.…”

Cooperative assistance of a sulfonamide in a proline-mediated direct asymmetric aldol addition

“…Recent research has seen the emergence of a variety of bifunctional sulfonamides based on several chiral scaffolds such as cinchona alkaloids, axially chiral biaryls, etc. 1 c ,2–4 Pioneering work by groups such as those of Wang 5 and Miura 6 have also illustrated the use of sulfonamides in combination with thioureas and squaramides, respectively, in constructing catalysts bearing multiple hydrogen-bond donors. Given the popularity of proline as a privileged organocatalytic scaffold, it is not surprising that researchers have also extensively explored proline sulfonamides to mediate a variety of asymmetric carbon–carbon bond forming transformations.…”

New bifunctional 1,3‐diamine organocatalysts derived from (+)‐camphoric acid for asymmetric Michael addition of 1,3‐dicarbonyl compounds to nitroolefins

“…In particular, the conjugate addition of 1,3‐dicarbonyl compounds to trans ‐β‐nitrostyrenes has attracted particular interest due to the reactivity of the resulting enantiopure products which are key intermediates for the preparation of a large number of pharmaceutical compounds. The asymmetric control of this reaction has been achieved with organocatalysts such as diamines, 8–14 amine‐thioureas, 15–20 and Cinchona derivatives 21–29 . Therefore, the development of chiral bifunctional hydrogen‐bonding organocatalysts, which can activate nucleophiles and electrophiles at the same time, have emerged as powerful organocatalysts.…”

“…The asymmetric control of this reaction has been achieved with organocatalysts such as diamines, [8][9][10][11][12][13][14] amine-thioureas, [15][16][17][18][19][20] and Cinchona derivatives. [21][22][23][24][25][26][27][28][29] Therefore, the development of chiral bifunctional hydrogen-bonding organocatalysts, which can activate nucleophiles and electrophiles at the same time, have emerged as powerful organocatalysts.…”