{"doi":"10.1002/chem.200400042","title":"Hydrogen‐Bonding Cooperativity: Using an Intramolecular Hydrogen Bond To Design a Carbohydrate Derivative with a Cooperative Hydrogen‐Bond Donor Centre","abstract":"<jats:title>Abstract</jats:title><jats:p>Neighbouring groups can be strategically located to polarise HO⋅⋅⋅OH intramolecular hydrogen bonds in an intended direction. A group with a unique hydrogen‐bond donor or acceptor character, located at hydrogen‐bonding distance to a particular OH group, has been used to initiate the hydrogen‐bond network and to polarise a HO⋅⋅⋅OH hydrogen bond in a predicted direction. This enhanced the donor character of a particular OH group and made it a cooperative hydrogen‐bond centre. We have proved that a five‐membered‐ring intramolecular hydrogen bond established between an amide NH group and a hydroxy group (1,2‐e,a), which is additionally located in a 1,3<jats:italic>‐cis‐</jats:italic>diaxial relationship to a second hydroxy group, can be used to select a unique direction on the six‐membered‐ring intramolecular hydrogen bond between the two axial OH groups, so that one of them behaves as an efficient cooperative donor. Talose derivative <jats:bold>3</jats:bold> was designed and synthesised to prove this hydrogen‐bonding network by NMR spectroscopy, and the mannopyranoside derivatives <jats:bold>1</jats:bold> and <jats:bold>2</jats:bold> were used as models to demonstrate the presence in solution of the 1,2‐(e,a)/five‐membered‐ring intramolecular hydrogen bond. Once a well‐defined hydrogen‐bond is formed between the OH and the amido groups of a pyranose ring, these hydrogen‐bonding groups no longer act as independent hydrogen‐bonding centres, but as hydrogen‐bonding arrays. This introduces a new perspective on the properties of carbohydrate OH groups and it is important for the de novo design of molecular recognition processes, at least in nonpolar media. Carbohydrates <jats:bold>1</jats:bold>–<jats:bold>3</jats:bold> have shown to be efficient phosphate binders in nonpolar solvents owing to the presence of cooperative hydroxy centres in the molecule.</jats:p>","journal":"Chemistry – A European Journal","year":2004,"id":43740,"datarank":2.6846944322431647,"base_score":3.9318256327243257,"endowment":3.9318256327243257,"self_citation_contribution":0.5897738449086489,"citation_network_contribution":2.094920587334516,"self_endowment_contribution":0.5897738449086489,"citer_contribution":2.094920587334516,"corpus_percentile":null,"corpus_rank":null,"citation_count":50,"citer_count":43,"citers_with_citation_signal":43,"citers_with_endowment":43,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":null,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":null,"fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":106281,"name":"Jason Martin","orcid":"0000-0003-2476-7639","position":1,"is_corresponding":false},{"id":207203,"name":"Jesús Jiménez‐Barbero","orcid":null,"position":2,"is_corresponding":false},{"id":207204,"name":"José Luis Chiara","orcid":null,"position":3,"is_corresponding":false},{"id":207205,"name":"Cristina Vicent","orcid":null,"position":4,"is_corresponding":false},{"id":207202,"name":"Virginie Vicente","orcid":null,"position":0,"is_corresponding":false}],"reference_count":0,"raw_metadata":{"has_enrichment":true,"base_score":3.9318256327243257,"endowment":3.9318256327243257,"datacite_reuse_total":0,"file_count":0,"downloads":0,"views":0,"has_version_chain":false,"is_dataset":false,"is_oa":false,"pmid":"15352107","pmcid":null,"openalex_id":"https://openalex.org/W1987057507","authors":[],"funders":[],"total_grants":0,"fwci":2.5251,"citation_percentile":0.8773987,"influential_citations":0,"citation_trend":[{"year":2013,"count":5},{"year":2014,"count":4},{"year":2015,"count":2},{"year":2016,"count":6},{"year":2017,"count":3},{"year":2018,"count":1},{"year":2019,"count":2},{"year":2020,"count":1},{"year":2021,"count":2},{"year":2022,"count":2},{"year":2024,"count":1}],"oa_status":"closed","license":"http://onlinelibrary.wiley.com/termsAndConditions#vor","oa_locations":[{"url":"https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fchem.200400042","host_type":"publisher"},{"url":"https://chemistry-europe.onlinelibrary.wiley.com/doi/pdf/10.1002/chem.200400042","host_type":"publisher"},{"url":"https://doi.org/10.1002/chem.200400042","host_type":"journal"},{"url":"https://pubmed.ncbi.nlm.nih.gov/15352107","host_type":"repository"},{"url":"http://hdl.handle.net/10261/30949","host_type":"repository"}],"fields_of_study":["Carbohydrate Chemistry and Synthesis","Glycosylation and Glycoproteins Research","Chemical Synthesis and Analysis","Chemistry","Medicine"],"mesh_terms":[],"keywords":["Intramolecular force","Hydrogen bond","Low-barrier hydrogen bond","Chemistry","Ring (chemistry)","Crystallography","Hydrogen","Stereochemistry","Molecule","Organic chemistry"],"sdg_mappings":[],"linked_datasets":[],"clinical_trials":[],"software_tools":[],"database_accessions":[],"source":"live","citation_network_status":"fetched"},"created_at":"2026-06-15T02:52:57.363147Z","pmid":null,"pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}