1,3-Dibromo-5,5-dimethylhydantoin as promoter for glycosylations using thioglycosides

Xu, Fuqiang; Pereira, Claney L.; Seeberger, Peter H.

doi:10.3762/bjoc.13.195

Cited by 8 publications

(3 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Among them, DBDMH, an inexpensive, nontoxic, and stable reagent, was the optimal promoter, giving a yield of 92% with commendable β-stereoselectivity (α/β < 1/20) (Table 1, entry 12). It is noteworthy that 1 equiv of the promoter DBDMH 29 or DIDMH 30 was used, while 2 equiv of other promoters was needed. This is the case because the two bromides on DBDMH or the two iodides on DIDMH can act as the thiophilic activator.…”

mentioning

confidence: 99%

Hydrogen-Bond-Mediated Aglycone Delivery: Synthesis of β-d-Fructofuranosides

Wang

Cui

et al. 2020

Org. Lett.

View full text Add to dashboard Cite

The construction of β-D-fructofuranosidic linkages is one of the major challenges in carbohydrate chemistry. In this work, we developed an efficient method for the synthesis of β-D-fructofuranosides by using a 6-picoloyl-protected fructofuranosyl thioglycoside as the glycosyl donor. Subsequently, we applied the approach to a wide variety of donors and acceptors. Furthermore, the successful synthesis of levantetrose confirmed its applicability in the multistep synthesis of oligosaccharides.

show abstract

mentioning

confidence: 99%

Hydrogen-Bond-Mediated Aglycone Delivery: Synthesis of β-d-Fructofuranosides

Wang

Cui

et al. 2020

Org. Lett.

View full text Add to dashboard Cite

show abstract

“…A promoter mixture based on 1,3-dibromo-5,5-dimethylhydantoin (DBDMH)/TfOH proved compatible with most PGs and offered a cheap and stable alternative for thioglycoside activation. 60 Still, despite the high solubility of DBDMH in CH 2 Cl 2 , the implementation of DBDMH in SPGS has only been reported in a mixture of CH 2 Cl 2 /dioxane. Phosphate and imidate donors are activated with TMSOTf in CH 2 Cl 2 (a stoichiometric or catalytic amount, respectively).…”

Section: The Glycosylation Stepmentioning

confidence: 99%

Recent Developments in Solid-Phase Glycan Synthesis

Huang

Delbianco

2022

Synthesis

View full text Add to dashboard Cite

Solid-phase glycans synthesis (SPGS) is a valuable approach to access broad collections of complex, well-defined oligo- and polysaccharides in short amount of time. The target structure is assembled following iterative cycles of glycosylation and deprotection, often aided by automated machines. To expand the scope of SPGS, new solid supports, linkers, glycosylation and deprotection reactions, and functionalization strategies are constantly being developed. Here we discuss the state of the art of SPGS, with particular focus on the chemistry happening on solid-phase. We highlight recent achievements as well as challenges to be addressed to expand the scope of SPGS even further.

show abstract

“…It was worth pointing out here that hydrolysis of 14 in wet CH 2 Cl 2 using N ‐iodosuccinimide (NIS) and silver triflate (AgOTf) as accelerants could cause partial cleavage of the benzylidene group and lead to a low reaction yield. However, we found that utilization of DBDMH [ 48 ] as the promoter could primely overcome foregoing problem and generate a high yield of the desired disaccharide hemiacetal product, which was then activated with trichloroacetonitrile (Cl 3 CCN) and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) to give trichloroacetimidate 15 in an overall yield of 74%. Thereafter, condensation of 15 with glucosaminyl acceptor 8 catalyzed by triflic acid (TfOH) in dry Et 2 O provided trisaccharide 4a in an excellent yield and complete α‐selectivity.…”

Section: Background and Originality Contentmentioning

confidence: 99%

Chemical Synthesis of an Octasaccharide Derivative Related to Group B StreptococcusCell‐Wall Polysaccharide

et al. 2022

View full text Add to dashboard Cite

Comprehensive Summary Group B Streptococcus (GBS) is the major pathogen that causes invasive infectious diseases in neonates and infants. The development of preventive and therapeutic strategies against GBS infection has been becoming the most pressing subject worldwide. Group B carbohydrate (GBC), the group B‐specific polysaccharide that distinguishes GBS with other streptococci species, has been identified as an attractive antigen for diagnosis and vaccine development because of its highly conservative tetra‐antennary structure. In this paper, a highly convergent [3 + 5] glycosylation strategy for efficient synthesis of an octasaccharide derivative related to GBC oligosaccharide unit II has been developed. In this synthesis, each glycosylation reaction was efficiently constructed with glycosyl imidates, especially trifluoroacetimidate, as donors, and each glycosidic bond was stereoselectively controlled via the neighboring group participation effect of acyl group on the 2‐O‐position of imidate donors or the solvent effect of Et2O. Furthermore, the aminoethylphosphate group was smoothly installed on the 6‐O‐position of d‐glucitol residue using the phosphoramidite method. After global deprotection, the target octasaccharide was successfully obtained from d‐glucitol in 29 steps with an overall yield of 1.37%. The free amino group installed on the aminoethylphosphate spacer of the target molecule enables its modification with functionalized biomolecules for further biological studies.

show abstract

1,3-Dibromo-5,5-dimethylhydantoin as promoter for glycosylations using thioglycosides

Cited by 8 publications

References 47 publications

Hydrogen-Bond-Mediated Aglycone Delivery: Synthesis of β-d-Fructofuranosides

Hydrogen-Bond-Mediated Aglycone Delivery: Synthesis of β-d-Fructofuranosides

Recent Developments in Solid-Phase Glycan Synthesis

Chemical Synthesis of an Octasaccharide Derivative Related to Group B StreptococcusCell‐Wall Polysaccharide

Contact Info

Product

Resources

About