Preparation of C-arylglycals via Suzuki–Miyaura cross-coupling of dihydropyranylphosphates

Abstract

The preparation of C-arylglycals has been accomplished employing the Suzuki-Miyaura cross-coupling reaction of dihydropyranylphosphates with arylboronate esters. The reaction is tolerant of both electron-donating (EDG) and electron-withdrawing (EWG) groups on the aromatic ring and affords the corresponding C-arylglycals in good to excellent yields (68-97%). Additionally, the ketene acetal phosphate derived from 6-deoxy-3,4-di-O-benzyl-L-rhamnal also couples efficiently to yield C-arylglycals in excellent yields.

Total Synthesis of Aryl C-Glycoside Natural Products: Strategies and Tactics

“…245 As a surrogate of glycal iodides, glycal phosphate 241 appeared, readily prepared from the corresponding 2-deoxy sugar lactone by enolization−phosphorylation (LiN(SiMe 3 ) 2 , (PhO) 2 P(O)Cl), which was used for the cross-coupling with aryl boronate esters (Scheme 94). 270 2.2.3.4. Cross-coupling at sp 3 -Hybridized Anomeric Carbon Center.…”

Current Applications of Suzuki–Miyaura Coupling Reaction in The Total Synthesis of Natural Products: An update

“…They developed an effective and practical method for the construction of C‐Glycosides 239 via one pot fashion. They exploited Pd‐catalyzed SMCR between carbohydrate‐derived ketene acetal phosphates 240 and arylboronate esters 241 in the presence of Na 2 CO 3 as a suitable base and Pd(PPh 3 ) 4 as catalyst to obtain C‐glycosides 239 in high to excellent yield (Scheme ) …”

“…They exploited Pd-catalyzed SMCR between carbohydrate-derived ketene acetal phosphates 240 and arylboronate esters 241 in the presence of Na 2 CO 3 as a suitable base and Pd(PPh 3 ) 4 as catalyst to obtain Cglycosides 239 in high to excellent yield (Scheme 37). [125] The rubrolides 242-245 are placed in a family of approximately 20 polysubstituted butenolides isolated mainly from ascidia (tunicates), [126] as well as from a marine fungus. [127] They have densely functionalized structures and exhibited highly biological properties involving antiviral, [128] antidiabetic, [128] antibacterial, [126a,e,d] anticancer, [126b] and anti-inflammatory [126c] activities.…”

Recent Advances in C-Glycoside Chemistry: Application, Synthesis and Reactions

“…Para a síntese de Cglicosídeos inclui o acoplamento cruzado Suzuki, que envolve a reação entre ácidos aril/vinil-borônicos ou organoboranos e halogenetos arila/vinilo ou triflatos catalisados por complexos de paládio. [167][168][169][170][171][172][173] Os glicais halogenados ou os estanil-glicais atuam como substratos potenciais no acoplamento de Stille com organoestanho ou organohaletos para fornecer C-glicosídeos. [174][175][176][177][178][179][180] Por outro lado, C-glicosídeos também pode ser sintetizado pela reação de acoplamento de Negishi de um composto de organozinco ou um halogeneto orgânico, catalisado por complexos de níquel ou paládio.…”