Generally Applicable Organocatalytic Tetrahydropyranylation of Hydroxy Functionalities with Very Low Catalyst Loading

Mike Kotke; Peter R. Schreiner

doi:10.1055/s-2007-965917

FEATUREARTICLE

Generally Applicable Organocatalytic Tetrahydropyranylation of Hydroxy Functionalities with Very Low Catalyst Loading

Mike Kotke, Peter R. Schreiner*
Institute of Organic Chemistry, Justus-Liebig University Gießen, Heinrich-Buff-Ring 58, 35392 Gießen, Germany
Fax: +49(641)9934309; e-Mail: prs@org.chemie.uni-giessen.de;

Abstract

Alle Artikel dieser Rubrik

Abstract

This paper presents the first acid-free, organocatalytic tetrahydropyran and 2-methoxypropene protection of alcohols, phenols, and other ROH derivatives utilizing privileged N,N′-bis[3,5-bis(trifluoromethyl)phenyl]thiourea and a polystyrene-bound analogue. The reactions are broadly applicably (also on preparative scale), in particular, to acid-sensitive substrates such as aldol products, hydroxy esters, acetals, silyl-protected alcohols, and cyanohydrins. The catalytic efficiency is truly remarkably with turnover numbers of 100,000 and turnover frequencies of up to 5700 h^-1 at catalyst loadings down to 0.001 mol%. The computationally supported mechanistic interpretation emphasizes the hydrogen bond assisted heterolysis of the alcohol and concomitant preferential stabilization of the oxyanion hole in the transition state.

Key words

acetals - alcohols - catalysis - protecting groups - supported catalysis

Volltext

Referenzen

References

1a Baumeyer G. Dittus G. Muller E. In Houben-Weyl 4th ed., Vol. VI/4: Muller G. Georg Thieme Verlag; Stuttgart: 1963. p.368-374

1b Miyashita M. Yoshikoshi A. Grieco PA. J. Org. Chem. 1977, 42: 3772

1c van Boom JH. Herscheid JDM. Reese CB. Synthesis 1973, 169

2 Branco LC. Afonso CAM. Tetrahedron 2001, 57: 4405

3 Kumar P. Dinesh CU. Reddy RS. Pandey B. Synthesis 1993, 1069

4 Campelo JM. Garcia A. Lafont F. Luna D. Marinas JM. Synth. Commun. 1992, 22: 2335

5 Hoyer S. Laszlo P. Orlovic M. Polla E. Synthesis 1986, 655

6 Hajipour AR. Pourmousavi SA. Ruoho AE. Synth. Commun. 2005, 35: 2889

7 Shirini F. Zolfigolb MA. Paktinat M. Synthesis 2006, 4252

8 Bartoli G. Giovannini R. Giuliani A. Marcantoni E. Massaccesi M. Merchiorre P. Paoletti M. Sambri L. Eur. J. Org. Chem. 2006, 1476

9 Kotke M. Schreiner PR. Tetrahedron 2006, 62: 434

10a Magnusson A. Hult K. Holmquist M. J. Am. Chem. Soc. 2001, 123: 4354

10b Tantillo DJ. Houk KN. J. Comput. Chem. 2002, 23: 84

11a Schreiner PR. Wittkopp A. Org. Lett. 2002, 4: 217

11b Wittkopp A. Schreiner PR. Chem. Eur. J. 2003, 9: 407

12 Schreiner PR. Chem. Soc. Rev. 2003, 32: 289

13a Wenzel AG. Lalonde MP. Jacobsen EN. Synlett 2003, 1919

13b Wenzel AG. Jacobsen EN. J. Am. Chem. Soc. 2002, 124: 12964

14 Fuerst DE. Jacobsen EN. J. Am. Chem. Soc. 2005, 127: 8964

15 Wittkopp A. Schreiner PR. In The Chemistry of Dienes and Polyenes Vol. 2: Rappoport Z. John Wiley & Sons; Chichester: 2000. p.1029-1088

16 Yoon TP. Jacobsen EN. Science 2003, 299: 1691

17a Okino T. Hoashi Y. Takemoto Y. Tetrahedron Lett. 2003, 44: 2817

17b Gabriella D. Herrera RP. Riccia A. Synlett 2004, 2374

17c Hoashi Y. Yabuta T. Takemoto Y. Tetrahedron Lett. 2004, 45: 9185

17d Okino T. Nakamura S. Furukawa T. Takemoto Y. Org. Lett. 2004, 6: 625

17e Berkessel A. Mukherjee S. Cleemann F. Muller TN. Lex J. Chem. Commun. 2005, 1898

17f Berkessel A. Cleemann F. Mukherjee S. Angew. Chem. Int. Ed. 2005, 44: 7466

17g Dove AP. Pratt RC. Lohmeijer BGG. Waymouth RM. Hedrick JL. J. Am. Chem. Soc. 2005, 127: 13798

17h Herrera RP. Sgarzani V. Bernardi L. Ricci A. Angew. Chem. Int. Ed. 2005, 44: 6576

17i Hoashi Y. Okino T. Takemoto Y. Angew. Chem. Int. Ed. 2005, 44: 4032

17j McCooey SH. Connon SJ. Angew. Chem. Int. Ed. 2005, 44: 6367

17k Mosse S. Alexakis A. Org. Lett. 2005, 7: 4361

17l Okino T. Hoashi Y. Furukawa T. Xu XN. Takemoto Y. J. Am. Chem. Soc. 2005, 127: 119

17m Sohtome Y. Hashimoto Y. Nagasawa K. Adv. Synth. Catal. 2005, 347: 1643

17n Taylor MS. Tokunaga N. Jacobsen EN. Angew. Chem. Int. Ed. 2005, 44: 6700

17o Wang J. Li H. Duan WH. Zu LS. Wang W. Org. Lett. 2005, 7: 4713

17p Wang J. Li H. Yu XH. Zu LS. Wang W. Org. Lett. 2005, 7: 4293

17q Xu XN. Furukawa T. Okino T. Miyabe H. Takemoto Y. Chem. Eur. J. 2005, 12: 466

17r Ye JX. Dixon DJ. Hynes PS. Chem. Commun. 2005, 4481

17s Yoon TP. Jacobsen EN. Angew. Chem. Int. Ed. 2005, 44: 466

17t Connon SJ. Chem. Eur. J. 2006, 12: 5418

17u Bernardi L. Fini F. Herrera RP. Ricci A. Sgarzani V. Tetrahedron 2006, 62: 375

17v Akiyama T. Itoh J. Fuchibe K. Adv. Synth. Catal. 2006, 348: 999

17w Dixon DJ. Richardson RD. Synlett 2006, 81

17x Hao L. Zu LS. Wang J. Wang W. Tetrahedron Lett. 2006, 47: 3145

17y Hoashi Y. Yabuta T. Yuan P. Miyabe H. Takemoto Y. Tetrahedron 2006, 62: 365

17z Sohtome Y. Takemura N. Iguchi T. Hashimoto Y. Nagasawa K. Synlett 2006, 144

(aa) Sohtome Y. Hashimoto Y. Nagasawa K. Eur. J. Org. Chem. 2006, 2894

(ab) Xu XN. Yabuta T. Yuan P. Takemoto Y. Synlett 2006, 137

(ac) Yalalov DA. Tsogoeva SB. Schmatz S. Adv. Synth. Catal. 2006, 348: 826

18 Tsogoeva SB. Yalalov DA. Hateley MJ. Weckbecker C. Huthmacher K. Eur. J. Org. Chem. 2005, 4995

19 Rueping M. Antonchick AP. Theissmann T. Angew. Chem. Int. Ed. 2006, 45: 6751

20a Hoffman CH. Wagner AF. Wilson AN. Walton E. Shunk CH. Wolf DE. Holly FW. Folkers K. J. Am. Chem. Soc. 1957, 79: 2316

20b Pflieger D. Muckensturm B. Tetrahedron 1989, 45: 2031

20c Hassner A. Näumann F. Chem. Ber. 1988, 121: 1823

20d Hon YS. Lee CF. Chen RJ. Szu PH. Tetrahedron 2001, 57: 5991

20e Hamada N. Sato T. Synlett 2004, 1802

21 Sigman MS. Vachal P. Jacobsen EN. Angew. Chem. Int. Ed. 2000, 39: 1279

22 Vachal P. Jacobsen EN. Org. Lett. 2000, 2: 867

23a Williams DR. Benbow JD. Tetrahedron Lett. 1990, 31: 5881

23b Kliegel W. Nanninga D. Monatsh. Chem. 1983, 114: 465

23c Tosco P. Bertinaria M. Di Stilo A. Cena C. Sorba G. Frutteroa R. Gascoa A. Bioorg. Med. Chem. 2005, 13: 4750

24 Miyabe H. Tuchida S. Yamauchi M. Takemoto Y. Synthesis 2006, 3295

25 Kjolberg O. Neumann K. Acta Chem. Scand. 1994, 48: 80

26a Pihko PM. Angew. Chem. Int. Ed. 2004, 43: 2062

26b Taylor MS. Jacobsen EN. Angew. Chem. Int. Ed. 2006, 45: 1520

27 Weiss KL. Alshafie G. Chapman JS. Mershon SM. Abou-Issa H. Clagett-Dame M. Robert W. Curley J. Bioorg. Med. Chem. Lett. 2001, 11: 1583

28 Becke AD. Phys. Rev. A: At., Mol., Opt. Phys. 1988, 38: 3098

29 Lee CT. Yang WT. Parr RG. Phys. Rev. B: Condens. Matter 1988, 37: 785

30 Frisch MJ. Trucks GW. Schlegel HB. Scuseria GE. Robb MA. Cheeseman JR. Montgomery JJA. Vreven T. Kudin KN. Burant JC. Millam JM. Iyengar SS. Tomasi J. Barone V. Mennucci B. Cossi M. Scalmani G. Rega N. Petersson GA. Nakatsuji H. Hada M. Ehara M. Toyota K. Fukuda R. Hasegawa J. Ishida M. Nakajima T. Honda Y. Kitao O. Nakai H. Klene M. Li X. Knox JE. Hratchian HP. Cross JB. Adamo C. Jaramillo J. Gomperts R. Stratmann RE. Yazyev O. Austin AJ. Cammi R. Pomelli C. Ochterski JW. Ayala PY. Morokuma K. Voth GA. Salvador P. Dannenberg JJ. Zakrzewski VG. Dapprich S. Daniels AD. Strain MC. Farkas O. Malick DK. Rabuck AD. Raghavachari K. Foresman JB. Ortiz JV. Cui Q. Baboul AG. Clifford S. Cioslowski J. Stefanov BB. Liu G. Liashenko A. Piskorz P. Komaromi I. Martin RL. Fox DJ. Keith T. Al-Laham MA. Peng CY. Nanayakkara A. Challacombe M. Gill PMW. Johnson B. Chen W. Wong MW. Gonzalez C. Pople JA. Gaussian version B.03 Gaussian Inc.; Pittsburgh: 2003.

31a Purvis GD. Bartlett RJ. J. Chem. Phys. 1981, 75: 1284

31b Urban M. Noga J. Cole SJ. Bartlett RJ. J. Chem. Phys. 1985, 83: 4041

31c Bartlett RJ. Watts JD. Kucharski SA. Noga J. Chem. Phys. Lett. 1990, 165: 513

31d Raghavachari K. Trucks GW. Pople JA. Head-Gordon M. Chem. Phys. Lett. 1989, 157: 479

32a Dunning TH. Peterson KA. Woon DE. In The Encyclopedia of Computational Chemistry Vol. 1: Schleyer PvR. Allinger NL. Clark T. Gasteiger J. Kollman PA. Schaefer HF. Schreiner PR. John Wiley & Sons; Chichester: 1998. p.88-115

32b Dunning TH. J. Chem. Phys. 1971, 55: 716

32c Dunning TH. J. Chem. Phys. 1989, 90: 1007