Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and Their Derivatives

Chapter 2 Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and Their Derivatives C. T. Bedford, C. T. Bedford Department of Chemistry, University College London, London, UKSearch for more papers by this author C. T. Bedford, C. T. Bedford Department of Chemistry, University College London, London, UKSearch for more papers by this author Book Editor(s):Mark Moloney, Mark Moloney University of Oxford, Mansfield Road, Oxford, UK, OX1 3TA United KingdomSearch for more papers by this author First published: 15 March 2024 https://doi.org/10.1002/9781119716846.ch2Book Series:Organic Reaction Mechanisms Series AboutPDFPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShareShare a linkShare onEmailFacebookTwitterLinkedInRedditWechat Summary Access to both stereoisomers of P-stereogenic phosphonothioates is provided by the chemoselective- and stereoselective alcoholysis of bi-2-naphthyl phosphonothioates. An internal nucleophilic catalyst-mediated cyclization for the synthesis of medium-sized lactones and lactams can be illustrated by the conversion in 90% yield of a bicyclic 9-hydroxyacid (30) into the 10-membered lactone (33) in CHCl3 at r.t. (Scheme 11). Activation of the carboxylic acid grouping of (30) by propanephosphonic acid anhydride (T3P) and diisopropylethylamine prompts the attack of it by the strategically located pyridine to form the N-acylium ion (31) which facilitates attack at C=O by the OH group to generate a TI (32), collapse of which forms the 10-membered lactone (33). References Allcock , H. R. and Walsh , E. J. , J. Am. Chem. Soc. , 94 , 4538 ( 1972 ). 10.1021/ja00768a021 CASWeb of Science®Google Scholar Movahed , F. S. , Sawant , D. N. , Bagal , D. B. , and Saito , S. , Synthesis-Stuttgart , 52 , 3253 ( 2020 ). 10.1055/s-0040-1707174 CASWeb of Science®Google Scholar Lai , M. , Wu , Z. , Su , F. , Yu , Y. , Jing , Y. , Kong , J. , Wang , Z. , Wang , S. , and Zhao , M. , Eur. J. Org. Chem. , 198 ( 2020 ). 10.1002/ejoc.201901630 Web of Science®Google Scholar Zhang , Q. , Cui , X. , Feng , T. , Zhang , Y. , Zhang , X. , and He , J. , Mol. Catal. , 484 , 110785 ( 2020 ). Google Scholar Kuwabara , K. , Maekawa , Y. , Minoura , M. , Maruyama , T. , and Murai , T. , J. Org. Chem. , 85 , 14446 ( 2020 ). 10.1021/acs.joc.0c00687 CASPubMedWeb of Science®Google Scholar Rapp , P. B. , Murai , K. , Ichiishi , N. , Leahy , D. K. , and Miller , S. J. , Org. Lett. , 22 , 168 ( 2020 ). 10.1021/acs.orglett.9b04119 CASPubMedWeb of Science®Google Scholar Szeler , K. , Williams , N. H. , Hengge , A. C. , and Kamerlin , S. C. L. , J. Org. Chem. , 85 , 6489 ( 2020 ). 10.1021/acs.joc.0c00441 CASPubMedWeb of Science®Google Scholar Lawer , A. , Rossi-Ashton , J. A. , Stephens , T. C. , Challis , B. J. , Epton , R. G. , Lynam , J. M. , and Unsworth , W. P. , Angew. Chem. Int. Ed. , 58 , 13942 ( 2019 ). 10.1002/anie.201907206 CASPubMedWeb of Science®Google Scholar Lawer , A. , Epton , R. G. , Stephens , T. C. , Palate , K. Y. , Lodi , M. , Marotte , E. , Lamb , K. J. , Sangha , J. K. , Lynam , J. M. , and Unsworth , W. P. , Chem. Eur. J. , 26 , 12674 ( 2020 ). 10.1002/chem.202002164 CASPubMedWeb of Science®Google Scholar Clarke , A. K. and Unsworth , W. P. , Chem. Sci. , 11 , 2876 ( 2020 ). 10.1039/D0SC00568A CASPubMedWeb of Science®Google Scholar Stephens , T. C. and Unsworth , W. P. , Synlett , 31 , 133 ( 2020 ). 10.1055/s-0037-1611500 CASWeb of Science®Google Scholar Zhao , Y. , Steiger , A. K. , and Pluth , M. D. , Chem. Commun. , 54 , 4951 ( 2018 ). 10.1039/C8CC02428F CASPubMedWeb of Science®Google Scholar Gilbert , A. K. , Zhao , Y. , Otteson , C. E. , and Pluth , M. D. , J. Org. Chem. , 84 , 14469 ( 2019 ). 10.1021/acs.joc.9b01873 CASPubMedWeb of Science®Google Scholar Zhou , S. C. , Mou , Y. J. , Liu , M. , Du , Q. , Ali , B. , Ramprasad , J. , Qiao , C. H. , Hu , L. F. , and Ji , X. Y. , J. Org. Chem. , 85 , 8352 ( 2020 ). 10.1021/acs.joc.0c00559 CASPubMedWeb of Science®Google Scholar Cerda , M. M. , Mancuso , J. L. , Mullen , E. J. , Hendon , C. H. , and Pluth , M. D. , Chem. Eur. J. , 26 , 5374 ( 2019 ). 10.1002/chem.201905577 Web of Science®Google Scholar Powell , C. R. , Foster , J. C. , Okyere , B. , Theus , M. H. , and Matson , J. B. , J. Am. Chem. Soc. , 138 , 13477 ( 2016 ). 10.1021/jacs.6b07204 CASPubMedWeb of Science®Google Scholar Powell , C. R. , Dillon , K. M. , and Matson , J. B. , Biochem. Pharmacol. ,. 149 , 110 ( 2018 ). 10.1016/j.bcp.2017.11.014 CASPubMedWeb of Science®Google Scholar Levinn , C. M. , Cerda , M.M. , and Pluth , M. D. , Acc. Chem. Res. , 52 , 2723 ( 2019 ). 10.1021/acs.accounts.9b00315 CASPubMedWeb of Science®Google Scholar Xu , S. , Hamsath , A. , Neill , D. L. , Wang , Y. , and Xian , M. , Chem. Eur. J. , 25 , 4005 ( 2019 ). 10.1002/chem.201804895 CASPubMedWeb of Science®Google Scholar Bora , P. , Chauhan , P. , Pardeshi , K. A. , and Chakrapani , H. , RSC Adv. , 8 , 27359 ( 2018 ). 10.1039/C8RA03658F CASPubMedWeb of Science®Google Scholar Shigenaga , A. , Chem. Pharm. Bull. , 67 , 1171 ( 2019 ). 10.1248/cpb.c19-00285 PubMedWeb of Science®Google Scholar Otaka , A. , Sato , K. , and Shigenaga , A. , Top. Curr. Chem. , 363 , 33 ( 2015 ). 10.1007/128_2014_586 CASPubMedWeb of Science®Google Scholar Shigenaga , A. , Org. Biomol. Chem. , 18 , 9706 ( 2020 ). 10.1039/D0OB01968B CASPubMedWeb of Science®Google Scholar Hutton , C. A. , Shang , J. , and Wille , U. , Chem. Eur. J. , 22 , 3163 ( 2016 ). 10.1002/chem.201503753 CASPubMedWeb of Science®Google Scholar Shang , J. , Thombare , V. J. , Charron , C. L. , Wille , U. , and Hutton , C. A. , Chem. Eur. J. , 27 , 1620 ( 2020 ). 10.1002/chem.202005035 PubMedWeb of Science®Google Scholar Foden , C. S. , Islam , S. , Fernandez-Garcia , C. , Maugeri , L. , Sheppard , T. D. , and Powner , M. W. , Science , 370 , 865 ( 2020 ). 10.1126/science.abd5680 CASPubMedWeb of Science®Google Scholar Canavelli , P. , Islam , S. , and Powner , M. W. , Nature , 571 , 546 ( 2019 ). 10.1038/s41586-019-1371-4 CASPubMedWeb of Science®Google Scholar Organic Reaction Mechanisms 2020 ReferencesRelatedInformation