Selective fluoroalkylation of organic compounds by tackling the "negative fluorine effect"

Topics in Current Chemistry

Volumn 308, Issue , 2012, Pages 25-44

  Zhang, Wei ^a   Ni, Chuanfa ^a   Hu, Jinbo ^a  

^a SHANGHAI INSTITUTE OF ORGANIC CHEMISTRY   (China)

Author keywords

Difluorocarbene; Fluorinated sulfones; Fluorinated sulfoximines; Fluoroalkylations; Negative fluorine effect

Indexed keywords

EID: 81855166715     PISSN: 03401022     EISSN: None     Source Type: Book Series    
DOI: 10.1007/128_2011_246     Document Type: Article

References (58)

1. Müller K, Faeh C, Diederich F (2007) Fluorine in pharmaceuticals: looking beyond intuition. Science 317:1881
2. Bégué J-P, Bonnet-Delpon D (2008) Bioorganic and medicinal chemistry of fluorine. Wiley, Hoboke
3. Hagmann WK (2008) The many roles for fluorine in medicinal chemistry. J Med Chem 51:4359
4. Prakash GKS, Chacko S (2008) Novel nucleophilic and electrophilic fluoroalkylation methods. Curr Opin Drug Discov Dev 11:793
5. Kirsch P (2004) Modern fluoroorganic chemistry: synthesis, reactivity, applications. Wiley-VCH, Weinheim
6. Banks RE, Smart BE, Tatlow JC (1994) Organofluorine chemistry: principles and commercial applications. Plenum, New York
7. O'Hagan D, Schaffrath C, Cobb SL, Hamilton JTG, Murphy CD (2002) Biochemistry: biosynthesis of an organofluorine molecule. Nature 416:279
8. Uneyama K (2006) Organofluorine chemistry. Blackwell, Oxford
9. Chambers RD (2004) Fluorine in organic chemistry. Blackwell, Oxford
10. Prakash GKS, Hu J (2007) Selective fluoroalkylations with fluorinated sulfones, sulfoxides, and sulfides. Acc Chem Res 40:921
11. Farnham WB (1996) Fluorinated carbanions. Chem Rev 96:1633
12. Prakash GKS, Yudin AK (1997) Perfluoroalkylation with organosilicon reagents. Chem Rev 97:757
13. Prakash GKS, Krishnamurti R, Olah GA (1989) Synthetic methods and reactions. 141. Fluoride-induced trifluoromethylation of carbonyl compounds with trifluoromethyltrimethylsilane (TMS-CF3). A trifluoromethide equivalent. J Am Chem Soc 111:393
14. Hagiwara T, Fuchikami T (1995) Difluoroalkylation of carbonyl compounds with (1,1-difluoroalkyl)silane derivatives. Synlett 7:717
15. Hu J, Zhang W, Wang F (2009) Selective difluoromethylation and monofluoromethylation reactions. Chem Commun 7465
16. Ni C, Hu J (2011) Selective nucleophilic fluoroalkylations facilitated by removable activation groups. Synlett 6:770
17. Bickelhaupt FM, Hermann HL, Boche G (2006) a-Stabilization of carbanions: fluorine is more effective than the heavier halogens. Angew Chem Int Ed 45:823
18. Faustov VI, D'yachenko AI, Nefedov OM (1979) Unstable organolithium halide compounds. Communication 7. Thermodynamic calculations of the mechanism of decomposition of organolithium halide compounds. Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya 2183
19. Boche G, Lohrenz JCW (2001) The electrophilic nature of carbenoids, nitrenoids, and oxenoids. Chem Rev 101:697
20. Capriati V, Florio S (2010) Anatomy of long-lasting love affairs with lithium carbenoids: past and present status and future prospects. Chem Eur J 16:4152
21. Stahly GP (1989) Nucleophilic addition of difluoromethyl phenyl sulfone to aldehydes and various transformations of the resulting alcohols. J Fluor Chem 43:53
22. Hine J, Porter JJ (1960) Formation of difluoromethylene from difluoromethyl phenyl sulfone and sodium methoxide. J Am Chem Soc 82:6178
23. Hu J (2009) Nucleophilic, radical, and electrophilic (phenylsulfonyl) difluoromethylations. J Fluor Chem 130:1130
24. Ni C, Li Y, Hu J (2006) Nucleophilic fluoroalkylation of epoxides with fluorinated sulfones. J Org Chem 71:6829
25. Ni C, Liu J, Zhang L, Hu J (2007) A remarkably efficient fluoroalkylation of cyclic sulfates and sulfamidates with PhSO2CF2H: facile entry into b-difluoromethylated or b-difluoromethylenated alcohols and amines. Angew Chem Int Ed 46:786
26. Fleming I (1976) Frontier orbitals and organic chemical reactions. Wiley, New York
27. Ho T-L (1977) Hard and soft acids and bases principle in organic chemistry. Academic, New York
28. Ni C, Zhang L, Hu J (2008) Nucleophilic fluoroalkylation of a, b-enones, arynes, and activated alkynes with fluorinated sulfones: probing the hard/soft nature of fluorinated carbanions. J Org Chem 73:5699
29. Prakash GKS, Hu J, Olah GA (2003) Preparation of tri-and difluoromethylsilanes via an unusual magnesium metal-mediated reductive tri-and difluoromethylation of chlorosilanes using tri-and difluoromethyl sulfides, sulfoxides, and sulfones. J Org Chem 68:4457
30. Prakash GKS, Hu J, Wang Y, Olah GA (2004) Nucleophilic difluoromethylation of primary alkyl halides using difluoromethyl phenyl sulfone as a difluoromethyl anion equivalent. Org Lett 6:4315
31. Prakash GKS, Hu J, Wang Y, Olah GA (2004) Difluoromethyl phenyl sulfone, a difluoromethylidene equivalent: use in the synthesis of 1,1-difluoro-1- alkenes. Angew Chem Int Ed 43:5203
32. Prakash GKS, Hu J, Mathew T, Olah GA (2003) Difluoromethyl phenyl sulfone as a selective difluoromethylene dianion equivalent: one-pot stereoselective synthesis of anti-2, 2-difluoropropane-1,3-diols. Angew Chem Int Ed 42:5216
33. Prakash GKS, Hu J, Wang Y, Olah GA (2005) Convenient synthesis of difluoromethyl alcohols from both enolizable and non-enolizable carbonyl compounds with difluoromethyl phenyl sulfone. Eur J Org Chem 2218
34. Ye J-D, Liao X, Piccirilli JA (2005) Synthesis of 20-C- difluoromethylribonucleosides and their enzymatic incorporation into oligonucleotides. J Org Chem 70:7902
35. Liu J, Ni C, Wang F, Hu J (2008) Stereoselective synthesis of a-difluoromethyl-b-amino alcohols via nucleophilic difluoromethylation with Me3SiCF2SO2Ph. Tetrahedron Lett 49:1605
36. Li Y, Hu J (2005) Facile synthesis of chiral a-difluoromethyl amines from N-(tertbutylsulfinyl) aldimines. Angew Chem Int Ed 44:5882
37. Liu J, Li Y, Hu J (2007) Stereoselective synthesis of di-and monofluoromethylated vicinal ethylenediamines with di-and monofluoromethyl sulfones. J Org Chem 72:3119
38. Li Y, Ni C, Liu J, Zhang L, Zheng J, Zhu L, Hu J (2006) Stereoselective nucleophilic monofluoromethylation of N-(tert-butanesulfinyl)imines with fluoromethyl phenyl sulfone. Org Lett 8:1693
39. Liu J, Zhang L, Hu J (2008) Stereoselective monofluoromethylation of N-tert-butylsulfinyl ketimines using pregenerated fluoro(phenylsulfonyl)methyl anion. Org Lett 10:5377
40. Reggelin M, Zur C (2000) Sulfoximines. Structures, properties, and synthetic applications. Synthesis 1:1
41. Boys ML, Collington EW, Finch H, Swanson S, Whitehead JF (1988) a-Fluoromethyln-methyl-phenylsulfoximine: a new fluoromethylenation reagent. Tetrahedron Lett 29:3365
42. Zhang W, Wang F, Hu J (2009) N-Tosyl-S-difluoromethyl-S- phenylsulfoximine: A new difluoromethylation reagent for S-, N-, and C-nucleophiles. Org Lett 11:2109
43. Noritake S, Shibata N, Makamura S, Toru T, Shiro M (2008) Fluorinated Johnson reagent for transfer-trifluoromethylation to carbon nucleophiles. Eur J Org Chem 3465
44. Nomura Y, Tokunaga E, Shibata N (2011) Inherent oxygen preference in enolate monofluoromethylation and a synthetic entry to monofluoromethyl ethers. Angew Chem Int Ed 50:1885
45. Zhang W, Huang W, Hu J (2009) Highly stereoselective synthesis of monofluoroalkenes from a-fluorosulfoximines and nitrones. Angew Chem Int Ed 48:9858
46. Zhang W, Hu J (2010) Efficient synthesis and ring-opening reactions of monofluorinated epoxides derived from a-fluorosulfoximines. Adv Synth Catal 352:2799
47. Zhao Y, Huang W, Zhu L, Hu J (2010) Difluoromethyl 2-pyridyl sulfone: a new gemdifluoroolefination reagent for aldehydes and ketones. Org Lett 12:1444
48. Prakash GKS, Ni C, Wang F, Hu J, Olah GA (2011) From difluoromethyl 2-pyridyl sulfone to difluorinated sulfonates: a protocol for nucleophilic difluoro(sulfonato)methylation. Angew Chem Int Ed 50:2559
49. Liu J, Hu J (2010) Highly diastereoselective synthesis of a-difluoromethyl amines from N-tert-butylsulfinyl ketimines and difluoromethyl phenyl sulfone. Chem Eur J 16:11443
50. Shen X, Zhang L, Zhao Y, Zhu L, Li G, Hu J (2011) Nucleophilic fluoromethylation of aldehydes with fluorobis(phenylsulfonyl)methane: the importance of strong Li-O coordination and fluorine substitution for C-C bond formation. Angew Chem Int Ed 50:2588
51. Zhu J, Zhang W, Zhang L, Liu J, Zheng J, Hu J (2010) Copper-mediated fluoroalkylation reactions with iododifluoroacetamides: controlling the selectivity among cross-coupling, intramolecular cyclization, and homocoupling reactions. J Org Chem 75:5505
52. Zhu J, Wang F, Huang W, Zhao Y, Ye W, Hu J (2011) Copper-mediated fluoroalkylation reactions with [(phenylsulfonyl)-difluoromethyl] trimethylsilane: synthesis of PhSO2CF2-containing allenes and alkynes. Synlett 7:899
53. Zhang L, Zheng J, Hu J (2006) 2-Chloro-2,2-difluoroacetophenone: a non-ODS-based difluorocarbene precursor and its use in the difluoromethylation of phenol derivatives. J Org Chem 71:9845
54. Zheng J, Li Y, Zhang L, Hu J, Meuzelaar GJ, Federsel H-J (2007) Chlorodifluoromethyl phenyl sulfone: a novel non-ozone-depleting substance-based difluorocarbene reagent for O-and N-difluoromethylations. Chem Commun 48:5149
55. Wang F, Zhang W, Zhu J, Li H, Huang K-W, Hu J (2011) Chloride ion-catalyzed generation of difluorocarbene for efficient preparation of gem-difluorinated cyclopropenes and cyclopropanes. Chem Commun 47:2411
56. Wang F, Luo T, Hu J, Wang Y, Krishnan HS, Jog PV, Ganesh SK, Prakash GKS, Olah GA (2011) Synthesis of gem-difluorinated cyclopropanes and cyclopropenes using TMSCF3 as a difluorocarbene source. Angew Chem Int Ed. 50:7153
57. Brahms LS, Dailey WP (1996) Fluorinated carbenes. Chem Rev 96:1585
58. Hudlicky M, Pavlath AE (1995) Chemistry of organic fluorine compounds II. American Chemical Society, Washington DC