Skip to main content
Log in

DIFLUORPHOS and SYNPHOS in asymmetric catalysis: Synthetic applications

  • Published:
Journal of Chemical Sciences Aims and scope Submit manuscript

Abstract

Enantiomerically pure diphosphines play an important role in various homogeneous metalcatalyzed asymmetric reactions. Over the last few years, our group has been involved in the design and synthesis of atropisomeric ligands named SYNPHOS and DIFLUORPHOS with complementary stereoelectronic properties. This paper shows the high catalytic performances of DIFLUORPHOS, SYNPHOS and SYNPHOS analogues for some C–H and C–C bond forming processes as well as for the synthesis of biorelevant targets.

Enantiomerically pure diphosphines play an important role in various homogeneous metal-catalysed asymmetric reactions. This study shows the high catalytic performances of atropisomeric ligands DIFLUORPHOS, SYNPHOS and SYNPHOS analogues for some C–H and C–C bond-forming processes as well as for the synthesis of biorelevant targets.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1.
Scheme 2.
Scheme 3.
Scheme 4.
Scheme 5.
Scheme 6.
Scheme 7.
Scheme 8.
Scheme 9.
Scheme 10.
Scheme 11.
Scheme 12.
Scheme 13.
Scheme 14.
Scheme 15.
Scheme 16.

Similar content being viewed by others

References

  1. Anastas P N and Kirchhoff M M 2002 Acc. Chem. Res. 35 686

    Google Scholar 

  2. (a) Noyori R 2002 Angew. Chem. Int. Ed. 41 2008; (b) Genet J P 2003 Acc. Chem. Res. 36 908; (c) de Vries J G and Elsevier C J 2006 Handbook of homogeneous hydrogenation (Weinheim, Germany: Wiley-VCH; (d) Shang G, Li W and Zhang X 2010 In Catalytic asymmetric synthesis (3rd ed.) I Ojima (ed) (New York: John Wiley & Sons) pp. 343–436; (e) Ager D J, de Vries A H M and de Vries J G 2012 Chem. Soc. Rev. 41 3340

  3. (a) McCarthy M and Guiry P J 2001 Tetrahedron 57 3809; (b) Tang W and Zhang X 2003 Chem. Rev. 103 3029

  4. (a) Duprat de Paule S, Champion N, Ratovelomanana-Vidal V, Genet J P, Dellis P Synkem, FP 0,112,499; 2001, PCT FR02/03146; (b) Duprat de Paule S, Champion N, Ratovelomanana-Vidal V, Genet J P, Dellis P, Synkem 2003 WO 03029259; (c) Duprat de Paule S, Jeulin S, Ratovelomanana-Vidal V, Genet J P, Champion N and Dellis P 2003 Tetrahedron Lett. 44 823; (d) Duprat de Paule S, Jeulin S, Ratovelomanana-Vidal V, Genet J P, Champion N and Dellis P 2003 Eur. J. Org. Chem. 1931; (e) Duprat de Paule S, Jeulin S, Ratovelomanana-Vidal V, Genet J P, Champion N, Deschaux G and Dellis P 2003 Org. Process Res. Dev. 7 399; (f) See also Pai C C, Li Y M, Zhou Z Y and Chan A S C 2002 Tetrahedron Lett. 43 2789

  5. (a) Jeulin S, Duprat de Paule S, Ratovelomanana-Vidal V, Genet J P, Champion N and Dellis P 2004 Angew. Chem. Int. Ed. 43 320; (b) Jeulin S, Duprat de Paule S, Ratovelomanana-Vidal V, Genet J P, Champion N and Dellis P 2004 Proc. Natl. Acad. Sci. USA 101 5799; (c) Genet J.-P, Ayad T, and Ratovelomanana-Vidal V 2014 Chem. Rev. DOI:cr-2013-003243

  6. Hatzenbuhler N T, Baudy R, Evrard D A, Failli A, Harrison B L, Lenicek S, Mewshaw R E, Saab A, Shah U, Sze J, Zhang M, Zhou D, Chlenov M, Kagan M, Golembieski J, Hornby G, Lai M, Smith D L, Sullivan K M, Schechter L E and Andree T H 2008 J. Med. Chem 51 6980

    Google Scholar 

  7. (a) Dupau P, Bruneau C and Dixneuf P H 1999 Tetrahedron: Asymmetry 10 3467; (b) Dupau P, Le Gendre P, Bruneau C and Dixneuf P H 1999 Synlett 11 1832; (c) Renaud J L, Dupau P, Hay A E, Guingouain M, Dixneuf P H and Bruneau C 2003 Adv. Synth. Catal. 345 230; (d) Pave G, Usse-Versluys S, Viaud-Massuard M C and Guillaumet G 2003 Org. Lett. 23 4253; (e) Holmberg P, Tedenborg L, Rosqvist S and Johansson A M 2005 Bioorg. Med. Chem. Lett. 15 747; (f) Holmberg P, Sohn D, Leideborg R, Caldirola P, Zlatoidsky P, Sverker H, Mohell N, Rosqvist S, Nordvall G, Johansson A M and Johansson R 2004 J. Med. Chem. 47 3927; (g) Zhou D, Hatzenbuhler N T, Gross J L, Harrison B L, Evrard D A, Chlenov M, Golembiesky J, Hornby G, Schechter L E, Smith D L, Andree T H and Stack G P 2007 Bioorg. Med. Chem. Lett. 17 3117; (h) Usse-Versluys S, Pave G, Guillaumet G and Viaud-Massuard M C 2001 Tetrahedron: Asymmetry 12 1689; (i) Fuganti C and Sacchetti A 2010 J. Mol. Catal. B: Enzym. 66 276

    Google Scholar 

  8. Wu Z, Ayad T and Ratovelomanana-Vidal V 2010 Org. Lett. 13 3782

  9. (a) Wang D S, Chen Q A, Lu S M and Zhou Y G 2012 Chem. Rev. 112 2557 and references cited herein; (b) Fleury-Brégeot N, De La Fuente V, Castillon S and Claver C 2010 Chem. Cat. Chem. 2 1346; (c) Kuwano R 2008 Heterocycles 76 909; (d) Glorius F. 2005 Org. Biomol. Chem. 3 4171; (d) Bartoszewicz A, Ahlsten N and Martin-Matute B 2013 Chem. Eur. J. 19 7274

  10. (a) Wang W B, Lu S M, Yang P Y, Han X W and Zhou Y G 2003 J. Am. Chem. Soc. 125 10536; (b) Lu S M, Wang Y Q, Han X W and Zhou Y G 2006 Angew. Chem. Int. Ed. 45 2260

  11. (a) Xu L, Lam K H, Ji J, Wu J, Fan Q H, Lo W H and Chan A S C 2005 Chem. Commun. 1390; (b) Wu J and Chan A S C 2006 Acc. Chem. Res. 39 711

  12. Qui L, Kwong F Y, Wu J, Lam W H, Chan S, Yu W Y, Li Y M, Guo R, Zhou Z and Chan A S C 2006 J. Am. Chem. Soc. 128 5955

  13. (a) Deport C, Buchotte M, Abecassis K, Tadaoka H, Ayad T, Ohshima T, Genet J P, Mashima K, Ratovelomanana-Vidal V 2007 Synlett 2243; (b) Tang W, Sun Y, Wang T, Fan Q, Lam K H and Chan A S C 2010 Org. Biomol. Chem. 8 3464

  14. Wang X B and Zhou Y G 2008 J. Org. Chem. 73 5640

    Google Scholar 

  15. Gou F R, Li W, Zhang X and Liang Y M 2010 Adv Synth. Catal. 352 2441

    Google Scholar 

  16. Zhang D Y, Wang D S, Wang M C, Yu C B, Gao K and Zhou Y G 2011 Synthesis 17 2796

  17. Zhang D Y, Yu C B, Wang M C, Gao and Zhou Y G 2012 Tetrahedron Lett. 53 2555

  18. Yamagata T, Tadaoka H, Nagata M, Hirao T, Kataoka Y, Ratovelomanana-Vidal V, Genet J P and Mashima K 2006 Organometallics 25 2505

  19. Tadaoka H, Cartigny D, Nagano T, Gosavi T, Ayad T, Genet J P, Ohshima T, Ratovelomanana-Vidal V and Mashima K 2009 Chem. Eur. J. 15 9990

    Google Scholar 

  20. (a) Chang G, Didiuk M T, Finneman J Y, Garigipati R S, Kelley R M, Perry D A, Ruggeri R B and Bechle B M 2004 WO 2004085401; (b) Gluchowski C 2004 EP 0422878A1; (c) Torisu K, Kobayashi K, Iwahashi M, Nakai Y, Onoda T, Nagase T, Sugimoto I, Okada Y, Matsumoto T, Nanbu F, Ohuchida S, Nakai H and Toda M 2004 Bioorg. Med. Chem. 12 5361; (d) Kuhl A, Kolkhof P, Telan L, Peters J G, Lustig K, Kast R, Muenter K, Stasch J P and Tinel H 2005 WO 2005028451; (e) Sikorski J A 2006 J. Med. Chem. 49 1; (f) Abraham C J, Paull D H, Scerba M T, Grebinski J W and Lectka T 2006 J. Am. Chem. Soc. 128 13370; (g) Eary C T, Jones Z S, Groneberg R D, Burgess L E, Mareska D A, Drew M D, Blake J F, Laird E R, Balachari D, O’Sullivan D, Allen A and Marsh V 2007 Bioorg. Med. Chem. Lett. 17 2608

    Google Scholar 

  21. Murata S, Sugimoto T and Matsuura S 1987 Heterocycles 26 763

  22. (a) Bianchini S, Barbaro P, Scapacci G, Farnetti E and Graziani M 1998 Organometallics 17 3308; (b) Bianchini C, Barbaro P and Scapacci G 2001 J. Organomet. Chem. 621 26; (c) Henschke J P, Burk M J, Malan C G, Herzberg D, Peterson J A, Wildsmith A J, Cobley C J and Casy G 2003 Adv. Synth. Catal. 345 300

  23. Qiu L, Kwong F Y, Wu J, LamWH, Chan S, Yu W Y, Li Y M, Guo R, Zhou Z and Chan A S C 2006 J. Am. Chem. Soc 128 5955

  24. Tang W, Xu L, Fan Q H, Wang J, Fan B, Zhou Z, Lam K H and Chan A S C 2009 Angew. Chem. Int. Ed. 48 9135

  25. MršićN, Jerphagnon T, Minnaard A J, Feringa B L and de Vries J G 2009 Adv. Synth. Catal. 351 2549

  26. Wang D S and Zhou Y G 2010Tetrahedron Lett. 51: 3014

    Google Scholar 

  27. (a) Cartigny D, Nagano T, Ayad T, Genet J P, Ohshima T, Mashima K and Ratovelomanana-Vidal V 2010 Adv. Synth. Catal. 352 1886; (b) Cartigny D, Berhal F, Nagano T, Phansavath P, Ayad T, Genet J P, Ohshima T, Mashima K and Ratovelomanana-Vidal V 2012 J. Org. Chem. 77 4544

  28. Nagano T, Iimuro A, Schwenk R, Ohshima T, Kita Y, Togni A and Mashima K 2012 Chem. Eur. J. 18 11578

    Google Scholar 

  29. (a) Phillipson J D, Roberts M F and Zenk M H 1985 The Chemistry and biology of isoquinoline alkaloids (Berlin: Springer); (b) Jack D and Williams R 2002 Chem. Rev. 102 1669; (c) Bentley K W 2006 Nat. Prod. Rep. 23 444

    Google Scholar 

  30. For selected examples, see: (a) Murahashi S I, Watanabe S and Shiota T 1994 J. Chem. Soc. Chem. Commun. 725; (b) Taniyama D, Hasegawa M, and Tomioka K 1999 Tetrahedron: Asymmetry 10 221; (c) Ooi T, Takeuchi M and Maruoka K 2001 Synthesis 1716; (d) Ito K, Akashi S, Saito B and Katsuki T 2003 Synlett 1809; (e) Taylor M S and Jacobsen E N 2004 J. Am. Chem. Soc. 126 10558; (f) Seayad J, Seayad A M and List B 2006 J. Am. Chem. Soc. 128 1086; (g) Sasamoto N, Dubs C, Hamashima Y and Sodeoka M 2006 J. Am. Chem. Soc. 128 14010; (h) Dubs C, Hamashima Y, Sasamoto N, Seidel T M, Suzuki S, Hashizume D and Sodeoka M 2008 J. Org. Chem. 73 5859; (i) Wang S, Onaran M B and Seto C T 2010 Org. Lett. 12 2690

  31. Willoughby C A and Buchwald S L 1994 J. Am. Chem. Soc. 116 8952

    Google Scholar 

  32. Uematsu N, Fujii A, Hashiguchi S, Ikariya T and Noyori R 1996 J. Am. Chem. Soc. 118 4916

  33. For asymmetric hydrogenation: (a) Morimoto T, Nakajima N and Achiwa K 1995 Tetrahedron: Asymmetry 6 75; (b) Morimoto T and Achiwa K 1995 Tetrahedron: Asymmetry 6 2661; (c) Morimoto T, Suzuki N and Achiwa K 1998 Tetrahedron: Asymmetry 9 183; (d) Zhu G and Zhang X 1998 Tetrahedron: Asymmetry 9 2415; (e) Cobley C J and Henschke J P 2003 Adv. Synth. Catal. 345 195; (f) Guiu E, Claver C, Benet-Buchholz J and Castillon S 2004 Tetrahedron: Asymmetry 15 3365; (g) Jackson M and Lennon I C 2007 Tetrahedron Lett. 48 1831; (h) Li C and Xiao J 2008 J. Am. Chem. Soc. 130 13208; (i) Yan P C, Xie J H, Hou G H, Wang L X and Zhou Q L 2009 Adv. Synth. Catal. 351 3243; (j) Lu S M, Wang Y G, Han X W and Zhou Y G 2009 Angew. Chem. Int. Ed. 45 2260; (k) Chang M, Li W and Zhang X 2011 Angew. Chem. Int. Ed. 50 10679; (l) Xie J H, Yan P C, Zhang Q Q, Yuan K X and Zhou Q L 2012 ACS Catal. 2 561; For asymmetric transfer hydrogenation, see: (m) Vedejs E, Trapencieris P and Suna E 1999 J. Org. Chem. 64 6724; (n) Mao J and Baker D C 1999 Org. Lett. 1 841; (o) Williams G D, Pike R A, Wade C E and Wills M 2003 Org. Lett. 5 4227; (p) Williams G D, Wade C E and Wills M 2005 Chem. Commun. 4735; (q) Szawkalo J and Czarnocki Z 2005 Monatsh. Chem. 136 1619; (r) Wu J, Wang F, Ma Y, Cui X, Cun L, Zhu J, Deng J and Yu B 2006 Chem. Commun. 1766; (s) Canivet J and Sss-Fink G 2007 Green Chem. 9 391; (t) Matharu D S, Martins J E D and Wills M 2008 Chem. Asian J. 3 1374; (u) Martins J E D, Clarkson G J and Wills M 2009 Org. Lett. 11 847; (v) Evanno L, Ormala J and Pihko P M 2009 Chem. Eur. J. 15 12963; (w) Martins J E D, Redondo M A C and Wills M 2010 Tetrahedron: Asymmetry 21 2258

  34. Berhal F,Wu Z, Zhang Z, Ayad T and Ratovelomanana-Vidal V 2012 Org. Lett. 14 3308 3308

    Google Scholar 

  35. Iimuro A, Yamaji K, Kandula S, Nagano T, Kita Y and Mashima K 2013 Angew. Chem. Int. Ed. 52 2046

  36. Reviews: (a) Trost B M and Krische M J 1998 Synlett 1; (b) Chianese A R, Lee S J and Gagne M R 2007 Angew. Chem. Int. Ed. 46 4042; (c) Michelet V, Toullec P Y, Genet J P 2008 Angew. Chem. Int. Ed. 47 4268; (d) Frstner A 2009 Chem. Soc. Rev. 38 3208. (e) Soriano E and Marco-Contelles J 2009 Acc. Chem. Res. 42 1026; (f) Pradal A, Toullec P Y and Michelet V 2011 Synthesis 1501; (g) Aubert C, Fensterbank L, Garcia P, Malacria M and Simonneau A 2011 Chem. Rev. 111 1954; (h) Marinetti A, Jullien H and Voituriez A 2012 Chem. Soc. Rev. 41 4884

  37. Jackowski O, Wang J, Xie X, Ayad T, Zhang Z and Ratovelomanana-Vidal V 2012 Org. Lett. 14 4006

    Google Scholar 

  38. Takaya Y, OsawaraM, Hayashi T, SakaiM and Miyaura N 1998 J. Am. Chem. Soc. 120 5579

  39. Reviews: (a) Hayashi T and Yamasaki K 2003 Chem. Rev. 103 2829; (b) Fagnou K and Lautens, M 2003 Chem. Rev. 103 169; (c) Hayashi T 2004 Pure Appl. Chem. 76 465; (d) Edwards H J, Hargrave J D, Penrose S D and Frost, C G 2010 Chem. Soc. Rev. 39 2093; (e) Miyaura M 2008 Bull. Chem. Soc. Jpn. 81 1535; (f) Harutyunyan S R, den Hartog T, Geurts K, Minnaard A J and Feringa B L 2008 Chem. Rev. 108 2824

  40. Reviews: (a) Shintani R and Hayashi T 2009 Aldrichim. Acta 42 31; (b) Defieber C, Grützmacher H and Carreira E 2008 Angew. Chem. Int. Ed. 47 4482

  41. (a) Korenaga T, Osaki R, Maenishi R and Sakai T 2009 Org. Lett. 11 2325; (b) Korenaga T, Maenishi R, Hayashi K and Sakai T 2010 Adv. Synth. Catal. 352 3247

  42. (a) Shintani R, Ueyama K, Yamada I and Hayashi T 2004 Org. Lett. 6 3425; (b) Shintani R, Duan W L, Nagano T, Okada A and Hayashi T 2005 Angew. Chem., Int. Ed. 44 4611; (c) Shintani R, Duan W L and Hayashi T 2006 J. Am. Chem. Soc. 128 5628; (d) Piras E, Lng F, Regger H, Stein D, Wrle M and Grtzmacher H 2006 Chem. Eur. J. 12 5849; (e) Nishikata T, Yamamoto Y and Miyaura N 2007 Chem. Lett. 36 1442; (f) Duan W L, Iwamura H, Shintani R and Hayashi T 2007 J. Am. Chem. Soc. 129 2130; (g) Duan W L, Shintani R and Hayashi T 2007 Tetrahedron 63 8529; (h) Luo Y and Carnell A J 2010 Angew. Chem. Int. Ed. 49 2750; (i) Thaler T, Guo L N, Steib A K, Raducan M, Karaghiosoff K, Mayer P and Knochel P 2011 Org. Lett. 13 3182

  43. Khand I U, Knox G R, Pauson P L and Watts W E 1971 J. Chem. Soc. Chem. Commun. 36

  44. Reviews: (a) Frhauf H W 1997 Chem. Rev. 97 523; (b) Geis O and Schmalz H G 1998 Angew. Chem. Int. Ed. 37 911; (c) Brummond K M and Kent J L 2000 Tetrahedron 56 3263; (d) Gibson S E and Stevenazzi A 2003 Angew. Chem. Int. Ed. 42 1800; (e) Blanco-Urgoiti J, Anorbe L, Perez-Serrano L, Dominguez G and Perez-Castells J 2004 Chem. Soc. Rev. 33 32

  45. (a) Ward R S 1990 Chem. Soc. Rev. 19 1; (b) Willis M C 1999 J. Chem. Soc., Perkin Trans. 1, 1765

  46. Kim D E, Lee B H, Rajagopalasarma M, Genet J P, Ratovelomanana-Vidal V and Jeong N 2008 Adv. Synth. Catal. 350 2695

    Google Scholar 

  47. Milanowski D J, Gustafson K R, Rashid M A, Pannell L K, McMahon J B and Boyd M R 2004 J. Org. Chem. 69 3036

    Google Scholar 

  48. Tone H, Buchotte M, Mordant C, Guittet E, Ayad T and Ratovelomanana-Vidal V 2009 Org. Lett. 11 1995

  49. (a) Kobayashi J, Ishibashi M, Nakamura H, Hirata Y, Yamasu T, Sasaki T and Ohizumi Y 1988 Experientia 44 800; (b) Kobayashi J 1989 J. Nat. Prod. 52 225

  50. Prévost S, Ayad T, Phansavath P and Ratovelomanana-Vidal. V 2011 Adv. Synth. Catal. 353 3213

  51. (a) Colin M, Gunard D, Guritte-Voegelein F and Potier P (Rhne-Poulenc Sant) 20 Jan 1988 Eur. Pat. Appl. EP 253 738 (Cl. C07D305/14), 17 Jul 1986 FR Appl. 86/10,400, 1988 Chem. Abstr. 109 22762w; (b) Mangatal L, Adeline M T, Gunard D, Guritte-Voegelein F and Potier P 1989 Tetrahedron 45 4177

  52. Wani M C, Taylor H L, Wall M E, Coggon P and McPhail A T 1971 J. Am. Chem. Soc. 93 2325

  53. Prévost S, Gauthier S, Mordant C, Touati AR, Lesot P, Savignac P, Ayad T, Phansavath P, Ratovelomanana-Vidal V and Genêt J P 2010 Tetrahedron: Asymmetry 21 1436

  54. Denis J N, Kanazawa A M and Greene A E 1994 Tetrahedron Lett. 35 105

    Google Scholar 

  55. Didier E, Fouque E, Taillepied I and Commerçon A 1994 Tetrahedron Lett. 35 234

  56. (a) Nakajima Y, Washizuka K, Sakurai M, Matsui S, Imamura E, Ueshima K, Yamamoto T, Yamamoto N, Ishikawa H, Nakano K, Unami N, Hamada K, Matsumura Y, Takamura F and Hattori K 2008 J. Med. Chem. 51 1925; (b) Imanishi M, Nakajima Y, Tomishima Y, Hamashima H, Washizuka K, Sakurai M, Matsui S, Imamura E, Ueshima K, Yamamoto T, Yamamoto N, Ishikawa H, Nakano K, Unami N, Hamada K, Matsumura Y, Takamura F and Hattori K 2008 J. Med. Chem. 51 4804; (c) Sawa M and Harada H 2006 Curr. Med. Chem. 13 25; (d) Devocelle M, Mortreux M, Agbossou F and Dormoy J P 1999 Tetrahedron Lett. 40 4551; (e) Cecchil R, Crocil T, Boigegrainz R, Boveril S, Baronil M, Boccardil G, Guimbardz J P and Guzzil U 1994 Eur. J. Med. Chem. 29 259

  57. Pautigny C, Debouit C, Vayron P, Ayad T and Ratovelomanana-VidalV 2010 Tetrahedron: Asymmetry 21 1382

  58. Koenig S G, Vandenbossche C P, Zhao H, Mousaw P, Singh S P and Bakale R P 2009 Org. Lett. 11 433

    Google Scholar 

Download references

Acknowledgements

We thank all the co-workers who have been involved in these projects and whose names appear in the references.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to VIRGINIE RATOVELOMANANA-VIDAL.

Rights and permissions

Reprints and permissions

About this article

Cite this article

PREVOST, S., AYAD, T., GENET, JP. et al. DIFLUORPHOS and SYNPHOS in asymmetric catalysis: Synthetic applications. J Chem Sci 126, 325–340 (2014). https://doi.org/10.1007/s12039-014-0571-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12039-014-0571-6

Keywords

Navigation