Alexander Dilman

Alexander Dilman
EducationHigher Chemical College of the Russian Academy of Sciences
Scientific career
FieldsOrganic chemistry, Organofluorine chemistry
WorkplacesN. D. Zelinsky Institute of Organic Chemistry
Sema Leybovich Ioffe, Vladimir Alexandrovich Tartakovsky
Websitedilmanlab.ru

Alexander Davidovich Dilman (Russian: Алекса́ндр Дави́дович Ди́льман) is a Russian organic chemist and is a professor of the Russian Academy of Sciences. Dilman is currently a Head of the Laboratory of Functional Organic Compounds at N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences (ZIOC RAS). Since 2022, he is a Corresponding Member of the Russian Academy of Sciences.

Biography

Dilman was born in Moscow in 1976. At the age of 15, he attended the Moscow Chemical Lyceum in order to dive deeper into chemistry. In 1993, Dilman attended the Higher Chemical College of the Russian Academy of Sciences. During his undergraduate research he studied the chemistry of nitro- and organosilicon compounds at the ZIOC RAS under the supervision of Vladimir Tartakovsky.

Dilman completed an internship in the group of Prof. Herbert Mayr [de] at LMU Munich in 2000. The results he obtained in Germany became a part of his dissertation. In 2001, he defended his Ph.D. thesis on the topic "Chemistry of N,N-bis(silyloxy)enamines" under the supervision of Prof. Sema Ioffe. During a post-doctoral internship in Prof. Henri Kagan's laboratory Dilman studied the chemistry of rhodium and iridium carbene complexes in 2002.

Dilman began to work in the field of organofluorine chemistry at ZIOC RAS in 2003. In 2008, he defended his Dr. Sci. dissertation connected with the development of new methods for the synthesis of fluorinated amines. In 2011 Dilman became the head of the Laboratory of Functional Organic Compounds at ZIOC RAS.[citation needed]

Research

Dilman's early works are related to the chemistry of silanes containing a perfluorinated group, alongside studies on reactivity to enamines, imines, iminium salts N-benzoyl hydrazones. A significant part of the research is devoted to the introduction of a trifluoromethyl group by means of a Ruppert-Prakash reagent, a difluoromethyl moiety from difluorocarbene and transformations of α,α-difluorinated phosphonium salts. The development of methods for the introduction of CF3– and CF2H– groups is important for medicinal chemistry.

Recently photoredox catalysis became the main research area of the Dilman group. Utilising visible light energy in chemical reactions allows many procedures to be more environmentally-friendly and widely available to organic chemists. Research of his group mainly involves development of approaches for radical functionalization of alkenes, imines, hydrazones and the activation of radical C–H bonds. Other research interests are connected with the activation of carboxylic acids under acridine photocatalytic conditions as well as photochemical transformations of polyfluorinated aryl sulfides.

Teaching

Since 2003, Dilman, together with William Smith has taught the course "Organic Synthesis" at ZIOC RAS. In 2009, he continued to lecture on this discipline together with his student V. V. Levin. A book based on the course, co-authored with W. A. Smith, was published in 2008.

Awards

References

  1. ↑ Dilman, A. D.; Lyapkalo, I. M.; Belyakov, P. A.; Ioffe, S. L.; Strelenko, Yu. A.; Tartakovsky, V. A. (2000). "N,N-Bis(tert-butyldimethylsilyloxy)aminobenzene as a new synthetic equivalent of nitrosobenzene". Russian Chemical Bulletin. 49 (9): 1649–1650. doi:10.1007/BF02495178. ISSN 1066-5285.
  2. ↑ Dilman, A. D.; Tishkov, A. A.; Lyapkalo, I. M.; Ioffe, S. L.; Strelenko, Yu A.; Tartakovsky, V. A. (1998). "Novel Convenient Method for the Synthesis of N,N-Bis(trimethylsilyloxy)enamines". Synthesis. 1998 (2): 181–185. doi:10.1055/s-1998-2019. ISSN 0039-7881.
  3. ↑ Дильман, Александр (2001). "Химия N, N-бис(силилокси)енаминов" [Chemistry of N,N-bis(silyloxy)enamines]. Moscow. Archived from the original on 2012-04-27.
  4. ↑ Dilman, Alexander D.; Tishkov, Alexander A.; Lyapkalo, Il'ya M.; Ioffe, Sema L.; Kachala, Vadim V.; Strelenko, Yury A.; Tartakovsky, Vladimir A. (2000). "Synthesis of N,N-bis(silyloxy)enamines with a functionalized double bond". Journal of the Chemical Society, Perkin Transactions 1 (17): 2926–2929. doi:10.1039/b004268o.
  5. ↑ Дильман, Александр (2008). "Новая методология синтетического использования силанов, содержащих перфторированную группу" [A new methodology for the synthetic use of silanes containing perfluorinated group]. Archived from the original on 2018-07-30.
  6. ↑ Levin, Vitalij V.; Dilman, Alexander D.; Belyakov, Pavel A.; Korlyukov, Alexander A.; Struchkova, Marina I.; Tartakovsky, Vladimir A. (2005). "On the interaction of silyl triflates with enamines: iminium ion formation versus silylation". Tetrahedron Letters. 46 (21): 3729–3732. doi:10.1016/j.tetlet.2005.03.144.
  7. ↑ Dilman, Alexander D.; Levin, Vitalij V.; Belyakov, Pavel A.; Struchkova, Marina I.; Tartakovsky, Vladimir A. (2006). "Synthesis of C 6 F 5 -Substituted Amines Containing Quaternary Carbon Atoms". Synthesis (3): 447–450. doi:10.1055/s-2006-926277. ISSN 0039-7881.
  8. ↑ Dilman, Alexander D.; Belyakov, Pavel A.; Korlyukov, Alexander A.; Struchkova, Marina I.; Tartakovsky, Vladimir A. (2005-07-01). "Synthesis of Pentafluorophenylmethylamines via Silicon Mannich Reaction". Organic Letters. 7 (14): 2913–2915. doi:10.1021/ol050845l. ISSN 1523-7060. PMID 15987168.
  9. ↑ Levin, Vitalij V.; Dilman, Alexander D.; Belyakov, Pavel A.; Struchkova, Marina I.; Tartakovsky, Vladimir A. (2006). "Chloride ion promoted nucleophilic pentafluorophenylation of imines". Tetrahedron Letters. 47 (50): 8959–8963. doi:10.1016/j.tetlet.2006.10.019.
  10. ↑ Levin, Vitalij V.; Kozlov, Mikhail A.; Song, Young-Hun; Dilman, Alexander D.; Belyakov, Pavel A.; Struchkova, Marina I.; Tartakovsky, Vladimir A. (2008). "Nucleophilic fluoroalkylation of iminium salts". Tetrahedron Letters. 49 (19): 3108–3111. doi:10.1016/j.tetlet.2008.03.043.
  11. ↑ Dilman, Alexander D.; Arkhipov, Dmitry E.; Levin, Vitalij V.; Belyakov, Pavel A.; Korlyukov, Alexander A.; Struchkova, Marina I.; Tartakovsky, Vladimir A. (2008-07-01). "Trifluoromethylation of N -Benzoylhydrazones". The Journal of Organic Chemistry. 73 (14): 5643–5646. doi:10.1021/jo800782w. ISSN 0022-3263. PMID 18558768.
  12. ↑ Gritsenko, Roman T.; Levin, Vitalij V.; Dilman, Alexander D.; Belyakov, Pavel A.; Struchkova, Marina I.; Tartakovsky, Vladimir A. (2009). "Trifluoromethylation of enamines under acidic conditions". Tetrahedron Letters. 50 (25): 2994–2997. doi:10.1016/j.tetlet.2009.03.187.
  13. ↑ Levin, Vitalij V.; Dilman, Alexander D. (2021). "One-pot synthesis of α-trifluoromethylstyrenes from aryl ketones and the Ruppert–Prakash reagent". Mendeleev Communications. 31 (5): 684–685. doi:10.1016/j.mencom.2021.09.030.
  14. ↑ Dilman, Alexander D.; Levin, Vitalij V. (2015). "Synthesis of organofluorine compounds using α-fluorine-substituted silicon reagents". Mendeleev Communications. 25 (4): 239–244. doi:10.1016/j.mencom.2015.07.001.
  15. ↑ Levin, Vitalij V.; Trifonov, Alexey L.; Zemtsov, Artem A.; Struchkova, Marina I.; Arkhipov, Dmitry E.; Dilman, Alexander D. (2014-12-05). "Difluoromethylene Phosphabetaine as an Equivalent of Difluoromethyl Carbanion". Organic Letters. 16 (23): 6256–6259. doi:10.1021/ol503225s. ISSN 1523-7060. PMID 25423177.
  16. ↑ Trifonov, Alexey L.; Levin, Vitalij V.; Struchkova, Marina I.; Dilman, Alexander D. (2017-10-06). "Difluoromethylation of Carboxylic Acids via the Addition of Difluorinated Phosphorus Ylide to Acyl Chlorides". Organic Letters. 19 (19): 5304–5307. doi:10.1021/acs.orglett.7b02601. ISSN 1523-7060. PMID 28915059.
  17. ↑ Trifonov, Alexey L.; Dilman, Alexander D. (2021-09-03). "Synthesis of Difluoroalkylated Heteroarenes via Difluorocarbene". Organic Letters. 23 (17): 6977–6981. doi:10.1021/acs.orglett.1c02603. ISSN 1523-7060. PMID 34428070.
  18. ↑ Levin, Vitalij V.; Dilman, Alexander D. (2019-06-21). "Visible-Light-Mediated Organocatalyzed Thiol–Ene Reaction Initiated by a Proton-Coupled Electron Transfer". The Journal of Organic Chemistry. 84 (12): 8337–8343. doi:10.1021/acs.joc.9b01331. ISSN 0022-3263. PMID 31129962.
  19. ↑ Kosobokov, Mikhail D.; Zubkov, Mikhail O.; Levin, Vitalij V.; Kokorekin, Vladimir A.; Dilman, Alexander D. (2020). "Fluoroalkyl sulfides as photoredox-active coupling reagents for alkene difunctionalization". Chemical Communications. 56 (66): 9453–9456. doi:10.1039/D0CC04617E. ISSN 1359-7345. PMID 32677653.
  20. ↑ Kostromitin, Vladislav S.; Zemtsov, Artem A.; Kokorekin, Vladimir A.; Levin, Vitalij V.; Dilman, Alexander D. (2021). "Atom-transfer radical addition of fluoroalkyl bromides to alkenes via a photoredox/copper catalytic system". Chemical Communications. 57 (42): 5219–5222. doi:10.1039/D1CC01609A. ISSN 1359-7345. PMID 33908970.
  21. ↑ Gladkov, Anton A.; Chernov, Grigory N.; Levin, Vitalij V.; Kokorekin, Vladimir A.; Dilman, Alexander D. (2021-12-17). "Photoredox Activation of Organozinc Reagents: Barbier-Type Reaction of Alkyl Halides with α-(Trifluoromethyl)styrenes". Organic Letters. 23 (24): 9645–9648. doi:10.1021/acs.orglett.1c03917. ISSN 1523-7060. PMID 34818011.
  22. ↑ Kostromitin, Vladislav S.; Sorokin, Artem O.; Levin, Vitalij V.; Dilman, Alexander D. (2023). "Aminals as powerful XAT-reagents: activation of fluorinated alkyl chlorides". Chemical Science. 14 (12): 3229–3234. doi:10.1039/D3SC00027C. ISSN 2041-6520. PMC 10034144. PMID 36970090.
  23. ↑ Supranovich, Vyacheslav I.; Levin, Vitalij V.; Dilman, Alexander D. (2019-06-07). "Radical Addition to N -Tosylimines via C–H Activation Induced by Decatungstate Photocatalyst". Organic Letters. 21 (11): 4271–4274. doi:10.1021/acs.orglett.9b01450. ISSN 1523-7060. PMID 31081641.
  24. ↑ Dmitriev, Igor A.; Levin, Vitalij V.; Dilman, Alexander D. (2021-11-19). "Boron Chelates Derived from N -Acylhydrazones as Radical Acceptors: Photocatalyzed Coupling of Hydrazones with Carboxylic Acids". Organic Letters. 23 (22): 8973–8977. doi:10.1021/acs.orglett.1c03501. ISSN 1523-7060. PMID 34752109.
  25. ↑ Panferova, Liubov I.; Zubkov, Mikhail O.; Kokorekin, Vladimir A.; Levin, Vitalij V.; Dilman, Alexander D. (2021-02-08). "Using the Thiyl Radical for Aliphatic Hydrogen-Atom Transfer: Thiolation of Unactivated C−H Bonds". Angewandte Chemie International Edition. 60 (6): 2849–2854. doi:10.1002/anie.202011400. ISSN 1433-7851. PMID 33146419.
  26. ↑ Zubkov, Mikhail O.; Kosobokov, Mikhail D.; Levin, Vitalij V.; Dilman, Alexander D. (2022-04-01). "Photocatalyzed Decarboxylative Thiolation of Carboxylic Acids Enabled by Fluorinated Disulfide". Organic Letters. 24 (12): 2354–2358. doi:10.1021/acs.orglett.2c00549. ISSN 1523-7060. PMID 35297636.
  27. ↑ Lipilin, Dmitry L.; Zubkov, Mikhail O.; Kosobokov, Mikhail D.; Dilman, Alexander D. (2024). "Direct conversion of carboxylic acids to free thiols via radical relay acridine photocatalysis enabled by N–O bond cleavage". Chemical Science. 15 (2): 644–650. doi:10.1039/D3SC05513B. ISSN 2041-6520. PMC 10762721. PMID 38179514.
  28. ↑ Rubanov, Zakhar M.; Levin, Vitalij V.; Dilman, Alexander D. (2024-04-19). "Dual Acridine/Decatungstate Photocatalysis for the Decarboxylative Radical Addition of Carboxylic Acids to Azomethines". Organic Letters. 26 (15): 3174–3178. doi:10.1021/acs.orglett.4c00778. ISSN 1523-7060. PMID 38587457.
  29. ↑ Zubkov, Mikhail O.; Kosobokov, Mikhail D.; Levin, Vitalij V.; Kokorekin, Vladimir A.; Korlyukov, Alexander A.; Hu, Jinbo; Dilman, Alexander D. (2020). "A novel photoredox-active group for the generation of fluorinated radicals from difluorostyrenes". Chemical Science. 11 (3): 737–741. doi:10.1039/C9SC04643G. ISSN 2041-6520. PMC 8146146. PMID 34123046.
  30. ↑ Panferova, Liubov I.; Dilman, Alexander D. (2021-05-21). "Light-Mediated Sulfur–Boron Exchange". Organic Letters. 23 (10): 3919–3922. doi:10.1021/acs.orglett.1c01080. ISSN 1523-7060. PMID 33929210.
  31. ↑ Panferova, Liubov I.; Zubkov, Mikhail O.; Kosobokov, Mikhail D.; Dilman, Alexander D. (2022-11-25). "Light-Promoted Dearylation of Perfluorinated Aryl Sulfides with N -Heterocyclic Carbene–Borane". Organic Letters. 24 (46): 8559–8563. doi:10.1021/acs.orglett.2c03585. ISSN 1523-7060. PMID 36351082.
  32. ↑ Смит, Вильям; Дильман, Александр (2009). Основы современного органического синтеза [Essentials of modern organic synthesis] (in Russian) (7th ed.). Москва: Издательство "Бином" (published 2024). ISBN 978-5-93208-434-2.
  33. ↑ "Протоколы и фотографии Менделеевских конференций 1990-2019 гг". www.chemeco.ru.
  34. ↑ "Система поддержки грантов Президента Российской Федерации. Победители конкурса 2007 года по государственной поддержке молодых российских ученых-кандидатов наук". grants.extech.ru. Retrieved 2024-11-30.
  35. ↑ "Liebig-Lectureship | Gesellschaft Deutscher Chemiker e.V." www.gdch.de (in German). Retrieved 2024-11-30.