Sulfur chemistry in action. New perspectives for organic synthesis

References

• Hoyle, C. E.; Bowman, C. N. Thiol-Ene Click Chemistry. Angew. Chem. Int. Ed. Engl. 2010, 49, 1540–1573. DOI: 10.1002/anie.200903924.
   PubMed Web of Science ®Google Scholar
• Cubbage, J. W.; Guo, Y.; McCulla, R. D.; Jenks, W. S. Thermolysis of Alkyl Sulfoxides and Derivatives: A Comparison of Experiment and Theory. J. Org. Chem. 2001, 66, 8722–8736. DOI: 10.1021/jo0160625.
   PubMed Web of Science ®Google Scholar
• Guignard, R. F.; Petit, L.; Zard, S. Z. A Method for the Contra-Thermodynamic Isomerization of Cyclic Trisubstituted Alkenes. Org. Lett. 2013, 15, 4178–4181. DOI: 10.1021/ol4018744.
   PubMed Web of Science ®Google Scholar
• Beletskaya, I. P.; Cheprakov, A. V. The Heck Reaction as a Sharpening Stone of Palladium Catalysis. Chem. Rev. 2000, 100, 3009–3066. DOI: 10.1021/cr9903048.
   PubMed Web of Science ®Google Scholar
• Cha, J. K.; Kulinkovich, O. G. The Kulinkovich Cyclopropanation of Carboxylic Acid Derivatives. Org. React. 2012, 77, 1–159.
   Google Scholar
• Connon, S. J.; Blechert, S. Recent developments in Olefin Cross-Metathesis. Angew. Chem. Int. Ed. Engl. 2003, 42, 1900–1923. DOI: 10.1002/anie.200200556.
   PubMed Web of Science ®Google Scholar
• Doyle, M. P. Catalytic Methods for Metal Carbene Transformations. Chem. Rev 1986, 86, 919–939.
   Web of Science ®Google Scholar
• Kobayashi, S.; Jorgensen, A. K. Cycloaddition Reactions in Organic Synthesis; Wiley: Weinheim, Germany, 2002.
   Google Scholar
• Radicals Encyclopedia of Radicals in Chemistry, Biology and Materials; Chatgilialoglu, C.; Studer, A., Eds.; Wiley-VCH: Weinheim, 2012.
   Google Scholar
• (a) McCombie, S. W.; Quiclet-Sire, B.; Zard, S. Z. Reflections on the Mechanism of the Barton-McCombie Deoxygenation and on Its Consequences. Tetrahedron 2018, 74, 4969–4979.
   Web of Science ®Google Scholar
  (b) For a review, see: McCombie, S. W.; Motherwell, W. B.; Tozer, M. J. The Barton–McCombie Reaction. Org. React. 2012, 77, 161–591. DOI: 10.1016/j.tet.2018.03.042.
   Google Scholar
• (a) Zard, S. Z. The Genesis of the Reversible Radical Addition-Fragmentation-Transfer of Thiocarbonylthio Derivatives from the Barton-McCombie Deoxygenation. A Brief account and Some Mechanistic Observations. Aust. J. Chem. 2006, 59, 663–668.
   Web of Science ®Google Scholar
  (b) Zard, S. Z. Discovery of the RAFT/MADIX Process. Mechanistic Insights and Polymer Chemistry Implications. Macromolecules 2020, 53, 8144–8159. DOI: 10.1021/acs.macromol.0c01441.
   Web of Science ®Google Scholar
• (a) Zard, S. Z. Radical Alliances: Solutions and Opportunities for Organic Synthesis. Helv. Chim. Acta 2019, 102, e1900134 ( DOI: 10.1002/hlca.201900134.).
   Web of Science ®Google Scholar
  (b) Quiclet-Sire, B.; Zard, S. Z. On the Strategic Impact of the Degenerative Transfer of Xanthates on Synthetic Planning. Isr. J. Chem. 2017, 57, 202–217.
   Web of Science ®Google Scholar
  (c) Quiclet-Sire, B.; Zard, S. Z. Fun with Radicals: Some New Perspectives for Organic Synthesis. Pure Appl. Chem. 2011, 83, 519–551.
   Web of Science ®Google Scholar
• Caine, D. In Comprehensive Organic Synthesis: Carbon-Carbon σ-Bond Formation; Trost, B. M., Fleming, I., Eds.; Pergamon: New York, 1991; Vol. 3.
   Google Scholar
• Zard, S. Z. The Xanthate Route to Ketones. When the Radical is Better than the Enolate. Acc. Chem. Res. 2018, 51, 1722–1733.
   PubMed Web of Science ®Google Scholar
• Bacqué, E.; Pautrat, F.; Zard, S. Z. A Flexible Strategy for the Divergent Modification of Pleuromutilin. Chem. Commun. 2002, 2312–2313. DOI: 10.1039/B206568A.
   PubMed Web of Science ®Google Scholar
• Zeise, W. C. J. Chem. Phys. 1822, 35, 173.
   Google Scholar
• Liard, A.; Quiclet-Sire, B.; Zard, S. Z. A Practical Method for the Reductive Cleavage of the Sulfide Bond in Xanthates. Tetrahedron Lett 1996, 37, 5877–5880.
   Web of Science ®Google Scholar
• (a) Han, S.; Zard, S. Z. A Modular Approach to Substituted Boc-Protected 3-Aminomethylpyrroles. Org. Lett. 2014, 16, 1992–1995.
   PubMed Web of Science ®Google Scholar
  (b) Han, S.; Zard, S. Z. A Convergent Route to Substituted Azetidines and to Boc-Protected 4-Aminomethylpyrroles. Tetrahedron 2015, 71, 3680–3689.
   Web of Science ®Google Scholar
• (a) Barton, D. H. R.; Jang, D. O.; Jaszberenyi, J. Cs. Hypophosphorous Acid and Its Salts - New Reagents for Radical Chain Deoxygenation, Dehalogenation and Deamination. Tetrahedron Lett. 1992, 33, 5709–5712.
   Web of Science ®Google Scholar
  (b) Boivin, J.; Jrad, R.; Juge, S.; Nguyen, V. T. On the Reduction of S-Alkyl-Thionocarbonates (Xanthates) with Phosphorus Compounds. Org. Lett. 2003, 5, 1645–1648. DOI: 10.1016/0040-4039(92)89012-2.
   PubMed Web of Science ®Google Scholar
• Denieul, M.-P.; Quiclet-Sire, B.; Zard, S. Z. Trifluoroacetonyl Radicals: A Versatile Approach to Trifluoromethyl Ketones. Chem. Commun. 1996, 2511–2512. DOI: 10.1039/cc9960002511.
   Web of Science ®Google Scholar
• Judd, T. C.; Brown, D. B. Access to Substituted Trifluoromethyl Ketones Using the Versatile Synthetic Intermediate (E)-1,1-Dimethyl-2-(1,1,1-Trifluoropropan-2-Ylidene)Hydrazine. Tetrahedron Lett. 2017, 58, 4455–4458.
   Web of Science ®Google Scholar
• Quiclet-Sire, B.; Yanagisawa, Y.; Zard, S. Z. A Direct, Versatile Route to Functionalized Trialkoxysilanes. Chem. Commun. (Camb) 2014, 50, 2324–2326. DOI: 10.1039/c3cc48570f.
   PubMed Web of Science ®Google Scholar
• (a) Ciriminna, R.; Fidalgo, A.; Pandarus, V.; Béland, F.; Ilharco, L. M.; Pagliaro, M. The Sol − Gel Route to Advanced Silica-Based Materials and Recent Applications. Chem. Rev. 2013, 113, 8, 6592–6620.
   Google Scholar
  (b) Cordes, D. B.; Lickiss, P. D.; Rataboul, F. Recent Developments in the Chemistry of Cubic Polyhedral Oligosilsesquioxanes. Chem. Rev. 2010, 110, 2081–2173.
   PubMed Web of Science ®Google Scholar
  (c) Llusar, M.; Sanchez, C. Inorganic and Hybrid Nanofibrous Materials Templated with Organogelators. Chem. Mater. 2008, 20, 782–820.
   Web of Science ®Google Scholar
  (d) Hu, L.-C.; Shea, K. J. Organo–silica hybrid functional nanomaterials: how do organic bridging groups and silsesquioxane moieties work hand-in-hand? Chem. Soc. Rev. 2011, 40, 688–695.
   PubMed Web of Science ®Google Scholar
  (e) Zou, H.; Wu, S.; Shen, J. Polymer/Silica Nanocomposites: Preparation, Characterization, Properties, and Applications. Chem. Rev. 2008, 108, 3893–3957.
   PubMed Web of Science ®Google Scholar
  (f) Kanamori, K.; Nakanishi, K. Controlled pore formation in organotrialkoxysilane-derived hybrids: from aerogels to hierarchically porous monoliths. Chem. Soc. Rev. 2011, 40, 754–770.
   PubMed Web of Science ®Google Scholar
  (g) Descalzo, A. B.; Martínez-Máñez, R.; Sancenón, F.; Hoffmann, K.; Rurack, K. The Supramolecular Chemistry of Organic–Inorganic Hybrid Materials. Angew. Chem. Int. Ed. 2006, 45, 5924–5948.
   PubMed Web of Science ®Google Scholar
  (h) Wight, A. P.; Davis, M. E. Design and Preparation of Organic − Inorganic Hybrid Catalysts. Chem. Rev. 2002, 102, 3589–3614.
   PubMed Web of Science ®Google Scholar
  (i) Lu, Z.-L.; Lindner, E.; Mayer, H. A. Applications of Sol-Gel-Processed Interphase Catalysts. Chem. Rev. 2002, 102, 3543–3578.
   PubMed Web of Science ®Google Scholar
  (j) Onclin, S.; Ravoo, B. J.; Reinhoudt, D. N. Engineering Silicon Oxide Surfaces Using Self-Assembled Monolayers. Angew. Chem., Int. Ed. 2005, 44, 6282–6304.
   PubMed Web of Science ®Google Scholar
  (k) Ulman, A. Formation and Structure of Self-Assembled Monolayers. Chem. Rev. 1996, 96, 1533–1554.
   PubMed Web of Science ®Google Scholar
• de Greef, M.; Zard, S. Z. A Unified, Radical Based Approach for the Synthesis of Spiroketals. Org. Lett. 2007, 9, 1773–1776. DOI: 10.1021/ol070488+.
   PubMed Web of Science ®Google Scholar
• Bergeot, O.; Corsi, C.; El Qacemi, M.; Zard, S. Z. S-(3-Chloro-2-Oxo-Propyl)-O-Ethyl Xanthate: A Linchpin Radical Coupling Agent for the Synthesis of Heterocyclic and Polycyclic Compounds. Org. Biomol. Chem. 2006, 4, 278–290. DOI: 10.1039/b514509k.
   PubMed Web of Science ®Google Scholar
• Li, J.-J. Name Reactions in Heterocyclic Chemistry; Wiley Interscience: New Jersey, 2005, Vol 1&2.
   Google Scholar
• Quiclet-Sire, B.; Zard, S. Z. Powerful Carbon-Carbon Bond Forming Reactions Based on a Novel Radical Exchange Process. Chemistry 2006, 12, 6002–6016. DOI: 10.1002/chem.200600510.
   PubMed Web of Science ®Google Scholar
• Dorokhov, V. S.; Quiclet-Sire, B.; Zard, S. Z. A Route to 5,5-Dithiospiroketals and to Long Chain Monomers from the Biomass. Org. Lett 2022, 24, 2878–2882.
   PubMed Web of Science ®Google Scholar
• Anthore-Dalion, L.; Liu, Q.; Zard, S. Z. A Radical Bidirectional Fragment Coupling Route to Unsymmetrical Ketones. J. Am. Chem. Soc. 2016, 138, 8404–8407. DOI: 10.1021/jacs.6b05344.
   PubMed Web of Science ®Google Scholar
• (a) Benetti, S.; Romagnoli, R.; De Risi, C.; Spalluto, G.; Zanirato, V. Mastering.beta.-Keto Esters. Chem. Rev. 1995, 95, 1065–1114.
   Web of Science ®Google Scholar
  (b) Casiraghi, G.; Battistini, L.; Curti, C.; Rassu, G.; Zanardi, F. The Vinylogous Aldol and Related Addition Reactions: Ten Years of Progress. Chem. Rev. 2011, 111, 3076–3154.
   PubMed Web of Science ®Google Scholar
  (c) Casiraghi, G.; Zanardi, F.; Appendino, G.; Rassu, G. The Vinylogous Aldol Reaction: A Valuable, yet Understated Carbon − Carbon Bond-Forming Maneuver. Chem. Rev. 2000, 100, 1929–1972.
   PubMed Web of Science ®Google Scholar
• Zard, S. Z. New Syntheses of Alkynes: A Tale of Serendipity and Design. Chem. Commun. 2002, 1555–1563. DOI: 10.1039/b203383f.
   PubMed Web of Science ®Google Scholar
• Anthore, L.; Li, S.; White, L. V.; Zard, S. Z. A Radical Solution to the Alkylation of the Highly Base-Sensitive 1,1-Dichloroacetone. Application to the Synthesis of Z-Alkenoates and E, E-Dienoates. Org. Lett. 2015, 17, 5320–5323.
   PubMed Web of Science ®Google Scholar
• (a) Anthore, L.; Zard, S. Z. Chemoselective Reduction: Xanthates as Traceless Precursors of Polyfunctionalized α,α-Dichloroketones. Org. Lett. 2017, 19, 5545–5548.
   PubMed Web of Science ®Google Scholar
  (b) Spiegel, D. A.; Wiberg, K. B.; Schacherer, L. N.; Medeiros, M. R.; Wood, J. L. J. Am. Chem. Soc. 2005, 127, 12513–12515.
   PubMed Web of Science ®Google Scholar
  (c) Medeiros, M. R.; Schacherer, L. N.; Spiegel, D. A.; Wood, J. L. Org. Lett. 2007, 9, 4427–4429.
   PubMed Web of Science ®Google Scholar
  (d) Boivin, J.; Nguyen, V. T. Beilstein J. Org. Chem. 2007, 3, 45.
   PubMedGoogle Scholar
  (e) Allais, F.; Boivin, J.; Nguyen, V. T. Beilstein J. Org. Chem. 2007, 3, 46. A similar System Has Also Been Developed by Renaud Using Methanol instead of Water:
   PubMedGoogle Scholar
  (f) Pozzi, D.; Scanlan, E. M.; Renaud, P. J. Am. Chem. Soc. 2005, 127, 14204–14205.
   PubMed Web of Science ®Google Scholar
• Quiclet-Sire, B.; Zard, S. Z. A Convenient, High Yielding Cleavage of the Thiocarbonyl Group in Xanthates. Bull. Korean Chem. Soc 2010, 31, 543–544.
   Web of Science ®Google Scholar
• (a) Verhe, R.; De Buyck, L.; De Kimpe, N.; Kudesia, V. P.; Schamp, N. Favorskii-Type Rearrangement of Chlorinated Acetylacetone Monomethyl Enol Ethers. Presumptive Evidence for a Cyclopropane Dimethyl Acetal Intermediate. J. Org. Chem. 1977, 42, 1256–1258.
   Web of Science ®Google Scholar
  (b) Schamp, N.; De Kimpe, N.; Coppens, W. The Favorskii Rearrangement of Dichlorinated Methylketones. Tetrahedron 1975, 31, 2081–2087.
   Web of Science ®Google Scholar
  (c) Schamp, N.; Coppens, W. On the Favorskii Rearrangememt of Dichloromethylketones. Tetrahedron Lett. 1967, 8, 2697–2699.
   Google Scholar
• Corbet, M.; de Greef, M.; Zard, S. Z. A Highly Conjunctive β-Keto Phosphonate: Application to the Synthesis of Pyridine Alkaloids Xestamines C, E, and H. Org. Lett 2008, 10, 253–256.
   PubMed Web of Science ®Google Scholar
• Goh, K. K. K.; Kim, S.; Zard, S. Z. A Free-Radical Variant for the Synthesis of Functionalized 1,5-Diketones. Org. Lett. 2013, 15, 4818–4821. DOI: 10.1021/ol402213k.
   PubMed Web of Science ®Google Scholar
• Selected monographs and books:(a) Hall, D. G., Ed. Boronic Acids: Preparation and Applications in Organic Synthesis, Medicine and Materials, Vols. 1 and 2; Wiley-VCH: New York, 2011.
   Google Scholar
  (b) Davidson, M. G., Hughes, A. K., Marder, T. B., Wade, K., Eds. Contemporary Boron Chemistry; Royal Society of Chemistry: Cambridge, 2000.
   Google Scholar
  (c) Hemming, D.; Fritzemeier, R.; Westcott, S. A.; Santos; W. L.; Steel, P. G. Copper-boryl Mediated Organic Synthesis. Chem. Soc. Rev. 2018, 47, 7477–7494.
   PubMed Web of Science ®Google Scholar
  (d) Akgun, B.; Hall, D. G. Boronic Acids as Bioorthogonal Probes for Site- Selective Labeling of Proteins. Angew. Chem. Int. Ed. 2018, 57, 13028–13044.
   PubMed Web of Science ®Google Scholar
• (a) Lopez-Ruiz, H.; Zard, S. Z.; Huang, Q.; Zard, S. Z. A Flexible Access to Highly Functionalised Boronates. A Radical Fragment Coupling Route to Geminal Bis(Boronates). Chem. Commun 2001, 2018, 20, 2618–2619.
   Google Scholar
  b Org. Lett. 5304–5308.
   Google Scholar
• Lamb, R.; Revil-Baudard, V. L.; Zard, S. Z. A Direct Approach to Orthogonally Protected α-Amino-Aldehydes. Org. Lett. 2019, 21, 6352–6356. DOI: 10.1021/acs.orglett.9b02237.
   PubMed Web of Science ®Google Scholar
• Chen, X.; Zard, S. Z. A Convergent Route to β-Amino Acids and to β-Heteroarylethylamines: An Unexpected Vinylation Reaction. Org. Lett. 2020, 22, 3628–3632. DOI: 10.1021/acs.orglett.0c01087.
   PubMed Web of Science ®Google Scholar
• Barbier, F.; Pautrat, F.; Quiclet-Sire, B.; Zard, S. Z. A Mild Radical Exchange Reaction of Xanthates with Bromine. Synlett 2002, 811–813. DOI: 10.1055/s-2002-25343.
   Web of Science ®Google Scholar
• Calculations for borylmethyl radical H2BCH2• give a radical stabilization energy (RSE) value of 10-11 kcal/mol, just slightly less than that of a benzyl radical (RSE = 14-15 kcal/mol). Oxygen substitutents reduce this stabilization to about 6-7 kcal/mol with. See:
   Google Scholar
  (a) Henry, D. J.; Parkinson, C. J.; Mayer, P. M.; Radom, L. Bond Dissociation Energies and Radical Stabilization Energies Associated with Substituted Methyl Radicals. J. Phys. Chem. A 2001, 105, 6750–6756.
   Web of Science ®Google Scholar
  (b) Walton, J. C.; McCarroll, A. J.; Chen, Q.; Carboni, B.; Nziengui, R. The Influence of Boryl Substituents on the Formation and Reactivity of Adjacent and Vicinal Free Radical Centers. J. Am. Chem. Soc. 2000, 122, 5455–5463.
   Web of Science ®Google Scholar
  (c) Coolidge, M. B.; Borden, W. T. Ab Initio Calculations of the Effects of Substituents on the Stabilization of Silyl Radicals versus Methyl Radicals. J. Am. Chem. Soc. 1988, 110, 2298–2299.
   Web of Science ®Google Scholar
  (d) Pasto, D. J. Radical Stabilization Energies of Disubstituted Methyl Radicals. A Detailed Theoretical Analysis of the Captodative Effect. J. Am. Chem. Soc. 1988, 110, 8164–8175.
   Web of Science ®Google Scholar
• Quiclet-Sire, B.; Zard, S. Z. Radical Instability in Aid of Efficiency. A Powerful Route to Highly Functional MIDA Boronates. J. Am. Chem. Soc. 2015, 137, 6762–6765. DOI: 10.1021/jacs.5b03893.
   PubMed Web of Science ®Google Scholar
• Huang, Q.; Michalland, J.; Zard, S. Z. Alternating Radical Stabilities. A Convergent Route to Terminal and Internal Boronates. Angew. Chem. Int. Ed. Engl. 2019, 58, 16936–16942. DOI: 10.1002/anie.201906497.
   PubMed Web of Science ®Google Scholar
• Sun, J.; Perfetti, M. T.; Santos, W. L. A Method for the Deprotection of Alkylpinacolyl Boronate Esters. J. Org. Chem 2011, 76, 3571–3575.
   PubMed Web of Science ®Google Scholar
• Michalland, J.; Zard, S. Z. A Modular Access to 1,2- and 1,3-Disubstituted Cyclobutylboronic Esters by Consecutive Radical Additions. Angew. Chem. Int. Ed 2022, 61, e202113333. DOI: 10.1002/anie.202113333.
   PubMed Web of Science ®Google Scholar
• (a) Miyaura, N.; Suzuki, A. Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds. Chem. Rev. 1995, 95, 2457–2483.
   Web of Science ®Google Scholar
  (b) Koshvandi, A. T. K.; Heravi, M. M.; Momeni, T. Current Applications of Suzuki–Miyaura Coupling Reaction in the Total Synthesis of Natural Products: An Update. Appl. Organomet. Chem. 2018, 32, e4210.
   Google Scholar
  (c) Brown, D. G.; Boström, J. Analysis of past and Present Synthetic Methodologies on Medicinal Chemistry: Where Have All the New Reactions Gone?: Miniperspective. J. Med. Chem. 2016, 59, 4443–4458.
   PubMed Web of Science ®Google Scholar
• Michalland, J.; Zard, S. Z. A Convergent, Stereoselective Route to Trisubstituted Alkenyl Boronates. Org. Lett. 2021, 23, 8018–8022. DOI: 10.1021/acs.orglett.1c03022.
   PubMed Web of Science ®Google Scholar
• Debien, L.; Quiclet-Sire, B.; Zard, S. Z. Allylic Alcohols: Ideal Radical Allylating Agents? Acc. Chem. Res. 2015, 48, 1237–1253. DOI: 10.1021/acs.accounts.5b00019.
   PubMed Web of Science ®Google Scholar