Advances in carbohydrate chemistry and biochemistry最新文献

{"title":"Stereoselective 1,2-cis glycosylation via intramolecular aglycone delivery: Opportunities and challenges.","authors":"Anindra Sharma, Danish Ansari, Vinod K Tiwari","doi":"10.1016/bs.accb.2025.10.001","DOIUrl":"10.1016/bs.accb.2025.10.001","url":null,"abstract":"<p><p>The stereoselective synthesis of 1,2-cis glycosidic linkages remains a vital challenge in carbohydrate chemistry owing to the lack of reliable anomeric directing effects. Intramolecular aglycon delivery (IAD) has emerged as an effective strategy to address this problem by employing temporary tethers that guide the glycosyl acceptor toward the anomeric center with high stereocontrol. As the methodology evolved, IAD has been advanced through the introduction of diverse acetal and ketal linkages, including dimethyl, dimethylsilyl, benzylidene, and iodoalkylidene tethers, enabling the efficient synthesis of challenging linkages such as β-mannopyranosides, β-L-rhamnosides, and α-glucosides. Further progress has been facilitated by the development of common alcohol protecting-group as tether, particularly p-methoxybenzyl (PMB) and 2-naphthylmethyl (NAP) groups, which have improved both the versatility and operational simplicity of IAD. A key advantage of this methodology lies in its ability to deliver exclusive 1,2-cis selectivity without generating anomeric mixtures, while also being amenable to iterative assembly of complex glycans. This chapter outlines the development, scope, and mechanistic insight of IAD, highlighting its limitations as well as its potential applications in the stereoselective synthesis of bioactive O-glycosides and structurally complex glycans.</p>","PeriodicalId":448936,"journal":{"name":"Advances in carbohydrate chemistry and biochemistry","volume":"88 ","pages":"1-46"},"PeriodicalIF":0.0,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145644361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Carbohydrate-modified carbonic anhydrase inhibitors: Advances and challenges.","authors":"Simone Giovannuzzi, Jean-Yves Winum, Claudiu T Supuran","doi":"10.1016/bs.accb.2025.09.003","DOIUrl":"10.1016/bs.accb.2025.09.003","url":null,"abstract":"<p><p>Carbonic anhydrases (CAs) are a family of metalloenzymes that catalyze the reversible conversion of carbon dioxide into bicarbonate and proton, a key reaction involved in numerous physiological and pathological processes. Over the past few decades, CAs have attracted considerable attention as therapeutic targets for conditions such as glaucoma, epilepsy, and cancer. The development of highly potent and selective inhibitors has consequently become a major focus, leading to the identification of novel drug candidates. Among the various strategies explored, the design of carbohydrate-based carbonic anhydrase inhibitors (CAIs) has proven to be particularly versatile for achieving selective CA targeting. The introduction of glycosyl groups as hydrophilic moieties into different CAI frameworks has resulted in the discovery of diverse sugar-based CAIs with significant inhibitory activity. This chapter provides an overview of carbohydrate-based CAIs reported to date.</p>","PeriodicalId":448936,"journal":{"name":"Advances in carbohydrate chemistry and biochemistry","volume":"87 ","pages":"111-167"},"PeriodicalIF":0.0,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145567022","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Carbohydrates and cardiovascular disease.","authors":"M Amin Mir, Bimal K Banik, Noushi Zaidi, Nouara Abdelli","doi":"10.1016/bs.accb.2025.09.002","DOIUrl":"10.1016/bs.accb.2025.09.002","url":null,"abstract":"<p><p>Carbohydrates are one of the most significant macronutrients in the human diet. They are necessary for energy metabolism and health. However, the prevalence and progression of cardiovascular diseases (CVD) have been associated with the intake of excessive refined sugars and carbohydrates. This paper provides an overview of the complex relationship between carbohydrates and CVD. Highlights include how simple sugars, starches, and fibers can affect the cardiovascular system. Excessive consumption of high glycemic index, and refined carbohydrates can lead to insulin resistance, dyslipidemia and chronic inflammation which all increase the risk of atherosclerosis and other cardiovascular diseases. On the contrary, fiber-rich carbohydrates from fruits, vegetables, and whole grains have been shown to have favorable effects on blood pressure, vascular function, and lipids, and contributes to a lower risk of CVD. The review also examines the role of functional foods, low glycemic index diets, and carbohydrate restriction, and other current dietary modifications for the prevention and treatment of CVD. Additionally, personalized diet therapy, as a potential new strategy for reducing carbohydrate-related CVD risk and new therapeutic possibilities where pharmacological agents have been developed to target these metabolic pathways.</p>","PeriodicalId":448936,"journal":{"name":"Advances in carbohydrate chemistry and biochemistry","volume":"87 ","pages":"25-42"},"PeriodicalIF":0.0,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145566966","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Visible-light-induced, photocatalyst-free generation of glycosyl radicals: Emerging routes for glycosylation.","authors":"Ramanand Das, Taraknath Kundu","doi":"10.1016/bs.accb.2025.10.004","DOIUrl":"10.1016/bs.accb.2025.10.004","url":null,"abstract":"<p><p>Stereoselective glycosylation remains one of the most powerful strategies for constructing biologically active molecules, yet precise control over anomeric selectivity continues to be a formidable challenge. Recently, visible-light-driven, photocatalyst-free protocols for generating glycosyl radicals have emerged as a reliable and sustainable alternative to stereoselective glycoside synthesis. The introduction of a wide variety of radical precursors has significantly broadened the scope of this chemistry, enabling access to structurally diverse and biologically relevant glycosidic architectures. These methods proceed under mild conditions, display excellent tolerance toward sensitive functional groups, and are inherently aligned with green chemistry principles. In this chapter, we discuss recent progress in photocatalyst-free glycosyl radical generation, with particular attention to innovative radical precursors and their applications in the construction of glycosides.</p>","PeriodicalId":448936,"journal":{"name":"Advances in carbohydrate chemistry and biochemistry","volume":"88 ","pages":"147-167"},"PeriodicalIF":0.0,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145644354","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Late stage O-glycosylation: A strategic gateway to complex therapeutic natural products.","authors":"Ram N Yadav, Luciana C Schmidt, Ashok Kumar Srivastava, Md Firoj Hossain, Vandana Singh","doi":"10.1016/bs.accb.2025.10.002","DOIUrl":"10.1016/bs.accb.2025.10.002","url":null,"abstract":"<p><p>Late-stage O-glycosylation has rapidly evolved into a paradigm-shifting strategy for the total synthesis of architecturally complex and pharmacologically privileged natural products. Unlike early-stage glycosylation, which is often constrained by protecting-group manipulations and linear synthetic planning, late-stage installation of glycosidic units offers unprecedented flexibility, enabling chemists to directly fine-tune biological performance at advanced synthetic stages. By strategically appending glycosyl residues onto fully elaborated aglycone scaffolds, this approach allows for rational modulation of solubility, metabolic stability, cell permeability, and target selectivity-properties that dictate clinical success yet are notoriously difficult to optimize through conventional synthetic modifications. This chapter highlights the conceptual evolution and methodological breakthroughs underpinning site- and stereoselective late-stage O-glycosylation. Recent innovations in transition-metal catalysis, organocatalytic activation, enzyme-mediated glycosyl transfer, and protecting-group-free tactics have expanded the synthetic toolbox, permitting precise glycosidic bond construction in densely functionalized settings. Case studies spanning anticancer anthracyclines, immunosuppressive macrolides, and antimicrobial glycopeptides illustrate how strategic glycosylation can reshape structure-activity relationships (SAR), improve therapeutic indices, and unlock access to glycoengineered analogues with superior drug-like profiles. Beyond synthetic utility, late-stage O-glycosylation provides a powerful lens through which chemical biology and medicinal chemistry converge. By transforming natural product frameworks into customizable molecular platforms, this strategy not only bridges the divide between synthetic innovation and translational drug discovery but also sets the stage for next generation glycomimetic therapeutics. Looking forward, integration of late-stage glycosylation with automated synthesis, chemoenzymatic platforms, and machine-learning-driven reaction design is poised to accelerate the discovery of tailor-made glycosylated drugs, cementing its role as a cornerstone of 21st-century molecular medicine.</p>","PeriodicalId":448936,"journal":{"name":"Advances in carbohydrate chemistry and biochemistry","volume":"88 ","pages":"47-125"},"PeriodicalIF":0.0,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145644239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Carbohydrates and cancer: A metabolic and epidemiological overview.","authors":"M Amin Mir, Bimal K Banik, Anuj Kumar, Ashish Kumar, Radhey Shyam","doi":"10.1016/bs.accb.2025.10.003","DOIUrl":"10.1016/bs.accb.2025.10.003","url":null,"abstract":"<p><p>Cancer causes dysregulation of apoptosis, a genetically controlled mechanism necessary for growth and homeostasis, which permits unchecked cell division and resistance to cell death. The Warburg effect, metabolic flexibility, and glucose reliance of malignant cells are highlighted in this chapter's analysis of the molecular interactions among insulin/IGF-1 signaling, carbohydrate metabolism, and tumor biology. We examine the data relating increased tumor survival, proliferation, and metastasis to hyperglycemia, hyperinsulinemia, and inflammatory cytokines. In the context of primary, secondary, and tertiary cancer prevention across a variety of tumor types, including colorectal, prostate, breast, and head and neck cancers, the epidemiological and experimental literature on dietary carbohydrates-from simple sugars to complex fibers-is assessed. There is discussion of mechanistic processes involving altered metabolism, hormonal regulation, and acidity of the microenvironment. While recognizing discrepancies and data gaps that need more study, the chapter emphasizes dietary modification-specifically, limiting carbohydrates and increasing fiber intake-as a promising adjunct in cancer prevention and survivorship.</p>","PeriodicalId":448936,"journal":{"name":"Advances in carbohydrate chemistry and biochemistry","volume":"87 ","pages":"1-24"},"PeriodicalIF":0.0,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145567031","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and biomedical applications of glycopolymers.","authors":"Mengfei Yin, Haohao Zhang, Tiantian Sun, Chao Cai","doi":"10.1016/bs.accb.2025.09.004","DOIUrl":"10.1016/bs.accb.2025.09.004","url":null,"abstract":"<p><p>As fundamental structural and functional units of biological systems, carbohydrates are recognized as indispensable to diverse physiological processes. Recent advances in the synthesis of well-defined glycopolymers enabled the development of biomimetic analogues that mimic natural glycans through cluster effects. These compounds have demonstrated critical significance in elucidating carbohydrate-mediated physiological mechanisms, identifying pathogenic pathways, and developing novel therapeutic strategies. Carbohydrate-protein interactions mediated by receptors such as ASGPR, DC-SIGN, M6PR, HA/NA, FimH, MR (CD206), Galectins, GLUTs, and BCR constitute the molecular basis for glycopolymer functionality and applications. Substantial explorations have been conducted in antimicrobial/antiviral applications and advanced drug delivery systems including gene therapy, antibody-protein conjugation, and small molecule encapsulation. These collective endeavors aim to expand the therapeutic frontiers of glycopolymers while offering transformative insights for next-generation pharmaceutical development.</p>","PeriodicalId":448936,"journal":{"name":"Advances in carbohydrate chemistry and biochemistry","volume":"87 ","pages":"43-110"},"PeriodicalIF":0.0,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145566973","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Emerging trends in stereoselective glycosyl ester synthesis.","authors":"Mittali Maheshwari, Nazar Hussain","doi":"10.1016/bs.accb.2025.09.001","DOIUrl":"10.1016/bs.accb.2025.09.001","url":null,"abstract":"<p><p>Glycosyl esters constitute a versatile class of molecules with significant roles in medicinal chemistry, natural product synthesis, and materials science. However, achieving their efficient synthesis continues to be a challenge, largely due to difficulties in controlling stereoselectivity and accommodating diverse functional groups. This chapter surveys recent developments in the stereoselective synthesis of glycosyl esters derived from various glycosyl donors. The discussion is organized around key activation strategies, Lewis acid catalysis, organocatalysis, and metal-free methods, highlighting their mechanistic foundations, catalytic efficiencies, and substrate scopes. This chapter aims to serve as a resource for researchers seeking to develop efficient, selective, and environmentally responsible routes to glycosyl esters.</p>","PeriodicalId":448936,"journal":{"name":"Advances in carbohydrate chemistry and biochemistry","volume":"88 ","pages":"127-145"},"PeriodicalIF":0.0,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145644241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"De novo asymmetric synthesis of the pyranoses-from monosaccharides to oligosaccharides: An update.","authors":"Sugyeom Kim, George A O'Doherty","doi":"10.1016/bs.accb.2024.10.004","DOIUrl":"10.1016/bs.accb.2024.10.004","url":null,"abstract":"<p><p>The various methods for the de novo asymmetric synthesis of the pyranose sugars are surveyed in this update of the 2013 Advances in Carbohydrate Chemistry and Biochemistry review. The survey begins with a general overview of the various de novo approaches to carbohydrates and defines the use of asymmetric catalysis for the de novo asymmetric synthesis of pyranoses. Next the application to pyranose-containing oligosaccharides is introduced via the use of a palladium-mediated glycosylation. The application of the diastereoselective palladium-catalyzed glycosylation in conjunction with the Achmatowicz approach towards the synthesis of oligosaccharides is presented. Finally, an alternative diastereoselective palladium-catalyzed glycosylation, followed by ring-closing methathesis to oligosaccharides is reviewed.</p>","PeriodicalId":448936,"journal":{"name":"Advances in carbohydrate chemistry and biochemistry","volume":"85 ","pages":"1-38"},"PeriodicalIF":0.0,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142690325","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The roadmap for sucrose - a very inexpensive raw product.","authors":"Sławomir Jarosz, Zbigniew Pakulski","doi":"10.1016/bs.accb.2024.10.002","DOIUrl":"10.1016/bs.accb.2024.10.002","url":null,"abstract":"<p><p>Sucrose, an inexpensive starting material available in virtually unlimited quantities, affords entry into a variety of novel and useful carbohydrate compounds. Selective protection of the secondary hydroxyl groups gives rise to a group of O-benzyl-protected intermediates that are useful in the synthesis of chiral phosphines and amino compounds of interest in the study of biological systems. The benzyl-protected fine chemicals are also key components in the synthesis of crown, thia-crown, and aza-crown compounds. Sophisticated molecular cages and molecular switches can be prepared from fine-tuned intermediates derived from selectively protected sucrose derivatives.</p>","PeriodicalId":448936,"journal":{"name":"Advances in carbohydrate chemistry and biochemistry","volume":"86 ","pages":"1-13"},"PeriodicalIF":0.0,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142696280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}