Stereospecific C–O sulfation via persulfate-induced 1,4-metallate migration

Blakemore, D. C. et al. Organic synthesis provides opportunities to transform drug discovery. Nat. Chem. 10, 383–394 (2018).Article 
CAS 
PubMed 

Google Scholar 
Fu, G. C. Transition-metal catalysis of nucleophilic substitution reactions: a radical alternative to SN1 and SN2 processes. ACS Cent. Sci. 3, 692–700 (2017).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Chen, C., Peters, J. C. & Fu, G. C. Photoinduced copper-catalysed asymmetric amidation via ligand cooperativity. Nature 596, 250–256 (2021).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Chen, J.-J. et al. Enantioconvergent Cu-catalysed N-alkylation of aliphatic amines. Nature 618, 294–300 (2023).Article 
CAS 
PubMed 

Google Scholar 
Hemmerich, S. in Handbook of Neurochemistry and Molecular Neurobiology: Neural Protein Metabolism and Function (eds Lajtha, A. & Banik, N.) 283–302 (Springer, 2007).Ernst, B. & Magnani, J. L. From carbohydrate leads to glycomimetic drugs. Nat. Rev. Drug Discovery 8, 661–677 (2009).Article 
CAS 
PubMed 

Google Scholar 
Kauffman, F. C. Sulfonation in pharmacology and toxicology. Drug Metab. Rev. 36, 823–843 (2004).Article 
CAS 
PubMed 

Google Scholar 
Gama, C. I. et al. Sulfation patterns of glycosaminoglycans encode molecular recognition and activity. Nat. Chem. Biol. 2, 467–473 (2006).Article 
CAS 
PubMed 

Google Scholar 
Huang, C. et al. Structures of the CCR5 N terminus and of a tyrosine-sulfated antibody with HIV-1 gp120 and CD4. Science 317, 1930–1934 (2007).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Al-Horani, R. A. & Desai, U. R. Chemical sulfation of small molecules—advances and challenges. Tetrahedron 66, 2907–2918 (2010).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Stone, M. J. & Payne, R. J. Homogeneous sulfopeptides and sulfoproteins: synthetic approaches and applications to characterize the effects of tyrosine sulfation on biochemical function. Acc. Chem. Res. 48, 2251–2261 (2015).Article 
CAS 
PubMed 

Google Scholar 
Wang, L. et al. Efficient platform for synthesizing comprehensive heparan sulfate oligosaccharide libraries for decoding glycosaminoglycan–protein interactions. Nat. Chem. 15, 1108–1117 (2023).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Ingram, L. J. & Taylor, S. D. Introduction of 2,2,2-trichloroethyl-protected sulfates into monosaccharides with a sulfuryl imidazolium salt and application to the synthesis of sulfated carbohydrates. Angew. Chem. Int. Ed. 45, 3503–3506 (2006).Article 
CAS 

Google Scholar 
Simpson, L. S. & Widlanski, T. S. A comprehensive approach to the synthesis of sulfate esters. J. Am. Chem. Soc. 128, 1605–1610 (2006).Article 
CAS 
PubMed 

Google Scholar 
Liu, C. et al. Fluorosulfate as a latent sulfate in peptides and proteins. J. Am. Chem. Soc. 145, 20189–20195 (2023).Article 
CAS 
PubMed 

Google Scholar 
Yue, S. et al. Dimethyl sulfate and diisopropyl sulfate as practical and versatile reagents in O-sulfation. Nat. Commun. 15, 1861 (2024).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Chapman, E., Best, M. D., Hanson, S. R. & Wong, C.-H. Sulfotransferases: structure, mechanism, biological activity, inhibition, and synthetic utility. Angew. Chem. Int. Ed. 43, 3526–3548 (2004).Article 
CAS 

Google Scholar 
Gilbert, E. E. The reactions of sulfur trioxide, and its adducts, with organic compounds. Chem. Rev. 62, 549–589 (1962).Article 
CAS 

Google Scholar 
Hoiberg, C. P. & Mumma, R. O. Preparation of sulfate esters. Reactions of various alcohols, phenols, amines, mercaptans, and oximes with sulfuric acid and dicyclohexylcarbodiimide. J. Am. Chem. Soc. 91, 4273–4278 (1969).Article 
CAS 

Google Scholar 
Johnson, J. R. & Van Campen, M. G. Jr. Organoboron compounds. IV. Reaction of tri-n-butylborine with peroxides and with oxygen. Mechanism of autoxidation. J. Am. Chem. Soc. 60, 121–124 (1938).Article 
CAS 

Google Scholar 
Brown, H. C. & Subba Rao, B. C. A new technique for the conversion of olefins into organoboranes and related alcohols. J. Am. Chem. Soc. 78, 5694–5695 (1956).Article 
CAS 

Google Scholar 
Brown, H. C., Kim, K.-W., Srebnik, M. & Singaram, B. Organoboranes for synthesis. 7. An improved general synthesis of primary amines from alkenes via hydroboration–organoborane chemistry. Tetrahedron 43, 4071–4078 (1987).Article 
CAS 

Google Scholar 
Draper, P. M., Chan, T. H. & Harpp, D. N. The chemistry of phosphorus and sulfur halides. Alkyl transfer from boranes. Tetrahedron Lett. 11, 1687–1688 (1970).Article 

Google Scholar 
Thomas, S. P., French, R. M., Jheengut, V. & Aggarwal, V. K. Homologation and alkylation of boronic esters and boranes by 1,2-metallate rearrangement of boronate complexes. Chem. Rec. 9, 24–39 (2009).Article 
CAS 
PubMed 

Google Scholar 
Wang, H., Jing, C., Noble, A. & Aggarwal, V. K. Stereospecific 1,2-migrations of boronate complexes induced by electrophiles. Angew. Chem. Int. Ed. 59, 16859–16872 (2020).Article 
CAS 

Google Scholar 
Sharma, H. A., Essman, J. Z. & Jacobsen, E. N. Enantioselective catalytic 1,2-boronate rearrangements. Science 374, 752–757 (2021).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Candeias, N. R., Montalbano, F., Cal, P. M. S. D. & Gois, P. M. P. Boronic acids and esters in the Petasis–borono Mannich multicomponent reaction. Chem. Rev. 110, 6169–6193 (2010).Article 
CAS 
PubMed 

Google Scholar 
Collins, B. S. L., Wilson, C. M., Myers, E. L. & Aggarwal, V. K. Asymmetric synthesis of secondary and tertiary boronic esters. Angew. Chem. Int. Ed. 56, 11700–11733 (2017).Article 
CAS 

Google Scholar 
Matteson, D. S. Asymmetric synthesis with boronic esters. Acc. Chem. Res. 21, 294–300 (1988).Article 
CAS 

Google Scholar 
Leonori, D. & Aggarwal, V. K. Lithiation–borylation methodology and its application in synthesis. Acc. Chem. Res. 47, 3174–3183 (2014).Article 
CAS 
PubMed 

Google Scholar 
Stymiest, J. L., Dutheuil, G., Mahmood, A. & Aggarwal, V. K. Lithiated carbamates: chiral carbenoids for iterative homologation of boranes and boronic esters. Angew. Chem. Int. Ed. 46, 7491–7494 (2007).Article 
CAS 

Google Scholar 
Zhang, L. et al. Catalytic conjunctive cross-coupling enabled by metal-induced metallate rearrangement. Science 351, 70–74 (2016).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Namirembe, S. & Morken, J. P. Reactions of organoboron compounds enabled by catalyst-promoted metalate shifts. Chem. Soc. Rev. 48, 3464–3474 (2019).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Kischkewitz, M., Okamoto, K., Mück-Lichtenfeld, C. & Studer, A. Radical-polar crossover reactions of vinylboron ate complexes. Science 355, 936–938 (2017).Article 
CAS 
PubMed 

Google Scholar 
Wang, D., Mück-Lichtenfeld, C. & Studer, A. 1,n-Bisborylalkanes via radical boron migration. J. Am. Chem. Soc. 142, 9119–9123 (2020).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Li, X. et al. Transition-metal-free C(sp2)–C(sp3) crosscoupling of α-(pseudo)halo aliphatic ketones with boronic acids via a 1,4-metallate shift. Nat. Synth. 2, 1211–1221 (2023).Article 

Google Scholar 
Hao, K. et al. Metal-free 1,3-boronate rearrangement to ketones driven by visible light. Angew. Chem. Int. Ed. 63, e202316481 (2024).Article 
CAS 

Google Scholar 
Zhang, J.-J. et al. One-pot synthesis of boron-doped polycyclic aromatic hydrocarbons via 1,4-boron migration. Angew. Chem. Int. Ed. 60, 2833–2838 (2021).Article 
CAS 

Google Scholar 
Mandal, S., Bera, T., Dubey, G., Saha, J. & Laha, J. K. Uses of K2S2O8 in metal-catalyzed and metal-free oxidative transformations. ACS Catal. 8, 5085–5144 (2018).Article 
CAS 

Google Scholar 
Behrman, E. J. The persulfate oxidation of phenols and arylamines (the Elbs and the Boyland–Sims oxidations). Org. React. 35, 421–511 (1988).He, Z., Song, F., Sun, H. & Huang, Y. Transition-metal-free Suzuki-type cross-coupling reaction of benzyl halides and boronic acids via 1,2-metalate shift. J. Am. Chem. Soc. 140, 2693–2699 (2018).Article 
CAS 
PubMed 

Google Scholar 
Deno, N. C. & Newman, M. S. Mechanism of sulfation of alcohols. J. Am. Chem. Soc. 72, 3852–3856 (1950).Article 
CAS 

Google Scholar 
Bi, H., Mass, R. & Just, G. Studies on anabolic steroids. 9. Tertiary sulfates of anabolic 17α-methyl steroids: synthesis and rearrangement. Steroids 57, 306–312 (1992).Article 
CAS 
PubMed 

Google Scholar 
Liu, C., Ji, C.-L., Hong, X. & Szostak, M. Palladium-catalyzed decarbonylative borylation of carboxylic acids: tuning reaction selectivity by computation. Angew. Chem. Int. Ed. 57, 16721–16726 (2018).Article 
CAS 

Google Scholar 
Li, C. et al. Decarboxylative borylation. Science 356, eaam7355 (2017).Article 
PubMed 
PubMed Central 

Google Scholar 
Berger, F. et al. Site-selective and versatile aromatic C–H functionalization by thianthrenation. Nature 567, 223–228 (2019).Article 
CAS 
PubMed 

Google Scholar 
Tu, J.-L. et al. Iron-catalyzed C(sp3)–H borylation, thiolation, and sulfinylation enabled by photoinduced ligand-to-metal charge transfer. J. Am. Chem. Soc. 145, 7600–7611 (2023).Article 
CAS 
PubMed 

Google Scholar 
Firth, J. D. et al. Light- and manganese-initiated borylation of aryl diazonium salts: mechanistic insight on the ultrafast time-scale revealed by time-resolved spectroscopic analysis. Chem. Eur. J. 27, 3979–3985 (2021).Article 
CAS 
PubMed 

Google Scholar 
Yang, C.-T. et al. Alkylboronic esters from copper-catalyzed borylation of primary and secondary alkyl halides and pseudohalides. Angew. Chem. Int. Ed. 51, 528–532 (2012).Article 
CAS 

Google Scholar 
Billingsley, K. L., Barder, T. E. & Buchwald, S. L. Palladium-catalyzed borylation of aryl chlorides: scope, applications, and computational studies. Angew. Chem. Int. Ed. 46, 5359–5363 (2007).Article 
CAS 

Google Scholar 
Choi, J. & Fu, G. C. Transition metal-catalyzed alkyl–alkyl bond formation: another dimension in cross-coupling chemistry. Science 356, eaaf7230 (2017).Article 
PubMed 
PubMed Central 

Google Scholar 
Chen, C. & Fu, G. C. Copper-catalysed enantioconvergent alkylation of oxygen nucleophiles. Nature 618, 301–307 (2023).Article 
CAS 
PubMed 
PubMed Central 

Google Scholar 
Bonet, A., Odachowski, M., Leonori, D., Essafi, S. & Aggarwal, V. K. Enantiospecific sp2–sp3 coupling of secondary and tertiary boronic esters. Nat. Chem. 6, 584–589 (2014).Article 
CAS 
PubMed 

Google Scholar 
Wang, D., Zhou, J., Hu, Z. & Xu, T. Deoxygenative haloboration and enantioselective chloroboration of carbonyls. J. Am. Chem. Soc. 144, 22870–22876 (2022).Article 
CAS 
PubMed 

Google Scholar 
Xi, Y. & Hartwig, J. F. Diverse asymmetric hydrofunctionalization of aliphatic internal alkenes through catalytic regioselective hydroboration. J. Am. Chem. Soc. 138, 6703–6706 (2017).Article 

Google Scholar 
Yang, K., Zhang, F., Fang, T., Zhang, G. & Song, Q. Stereospecific 1,4-metallate shift enables stereoconvergent synthesis of ketoximes. Angew. Chem. Int. Ed. 58, 13421–13426 (2019).Article 
CAS 

Google Scholar 
Yang, Q. et al. Holistic prediction of the pKa in diverse solvents based on a machine-learning approach. Angew. Chem. Int. Ed. 59, 19282–19291 (2020).Article 
CAS 

Google Scholar 

Hot Topics

Related Articles