Bismuth Compounds in Organic
Synthesis: Synthesis of Dioxanes, Dioxepines, and Dioxolanes Catalyzed
by Bismuth(III) Triflate

Daniel M. Podgorski; Scott W. Krabbe; Long N. Le; Paul R. Sierszulski; Ram S. Mohan

doi:10.1055/s-0030-1258148

PAPER

Bismuth Compounds in Organic Synthesis: Synthesis of Dioxanes, Dioxepines, and Dioxolanes Catalyzed by Bismuth(III) Triflate

Daniel M. Podgorski, Scott W. Krabbe, Long N. Le, Paul R. Sierszulski, Ram S. Mohan*
Laboratory for Environmentally Friendly Organic Synthesis, Department of Chemistry, Illinois Wesleyan University, Bloomington, IL 61701, USA
Fax: +1(309)5563864; e-Mail: rmohan@iwu.edu;

Abstract

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Abstract

A simple method for the synthesis of 1,3-dioxolanes from carbonyl compounds has been developed using 1,2-bis(trimethylsilyloxy)ethane in the presence of bismuth(III) triflate as a catalyst. The bismuth(III) triflate catalyzed synthesis of a range of dioxanes and dioxepines has also been developed. In these latter cases, the carbonyl compound is treated with a diol, and triethyl orthoformate is used as a water scavenger. All these methods avoid the use of a Dean-Stark trap.

Key words

aldehydes - ketones - protection - cyclic acetals - 1,2-bis(trimethylsilyloxy)ethane

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Referenzen

References

1a Greene TW. Wuts PGM. Protective Groups in Organic Synthesis 3rd ed.: Wiley; New York: 1999.

1b Hanson JR. Protecting Groups in Organic Synthesis Blackwell; Malden / MA: 1999.

1c Kocienski PJ. Protecting Groups Georg Thieme Verlag; Stuttgart: 1994.

1d Bergstrom RG. In The Chemistry of Ethers, Crown Ethers, Hydroxyl Groups and Their Sulphur Analogues Suppl. E, Part 2: Patai S. Wiley; New York: 1980. Chap. 20.

1e Schnitz E. Eichorn I. In The Chemistry of the Ether Linkage Patai S. Wiley; New York: 1967. Chap. 7.

2a We have reported the one-pot allylation of cyclic acetals followed by in situ derivatization with anhydrides to yield highly functionalized esters: Spafford MJ. Christensen JE. Huddle MG. Lacey JR. Mohan RS. Aust. J. Chem. 2008, 61: 419

For other examples of acetal allylation, see:

2b Bartlett PA. Johnson WS. Elliott JD. J. Am. Chem. Soc. 1983, 105: 2088

2c Denmark SE. Almstead NG. J. Org. Chem. 1991, 56: 6458

2d Denmark SE. Almstead NG. J. Org. Chem. 1991, 56: 6485

2e Egami Y. Takayanagi M. Tanino K. Kuwajima I. Heterocycles 2000, 52: 583

2f Morelli C. Durì L. Saladino A. Speranza G. Manitto P. Synthesis 2004, 3005

2g Jiang S. Agoston GE. Chen T. Cabal M.-P. Turos E. Organometallics 1995, 14: 4697

2h Hunter R. Michael JP. Tomlinson GD. Tetrahedron 1994, 50: 871

2i Carrel F. Giraud S. Spertini O. Vogel P. Helv. Chim. Acta 2004, 87: 1048

2j Suzuki T. Oriyama T. Synth. Commun. 1999, 29: 1263

3a Daignault RA. Eliel EL. Org. Synth. Collect. Vol. V Wiley; New York: 1973. p.303

3b Caserio FF. Roberts JD. J. Am. Chem. Soc. 1958, 80: 5837

3c Fieser LF. Stevenson R. J. Am. Chem. Soc. 1954, 76: 1728

3d Howard EG. Lindsey RV. J. Am. Chem. Soc. 1960, 82: 158

3e Dauben WG. Gerdes JM. Look GC. J. Org. Chem. 1986, 51: 4964

For some recent examples, see:

4a DeAngelis A. Panne P. Yap GPA. Fox JM. J. Org. Chem. 2008, 73: 1435

4b TsOH-SiO₂: Borah KJ. Phukan M. Borah R. Synth. Commun. 2008, 38: 3082

4c La(NO₃)₃×6H₂O: Srinivasulu N. Suryakiran N. Rajesh K. Reddy SM. Venkateswarlu Y. Synth. Commun. 2008, 38: 1753

4d H₃PW₁₂O₄₀: Yang S. Zhang Y. Du X. Merle PG. Rare Met. 2008, 27: 89

4e TfOH and formalin: Du Y. Tian F. Catal. Commun. 2007, 8: 2012

4f Polystyrenesulfonic acid: Polshettiwar V. Varma RS. J. Org. Chem. 2007, 72: 7420

4g Ammonium triflate: Karimi B. Ghoreishi-Nezhad M. J. Mol. Catal. A: Chem. 2007, 277: 262

4h Ce(OTf)₃: Ono F. Takenaka H. Fujikawa T. Mori M. Sato TJ. Synthesis 2009, 1318

5a Ethylene glycol/TMSCl: Chan TH. Brook MA. Chaly T. Synthesis 1983, 203

5b AlPO₄: Bautista FM. Campelo JM. García A. Leon J. Luna D. Marinas JM. J. Prakt. Chem. 1994, 336: 620

5c CdI₂: Laskar DD. Prajapati D. Sandhu JS. Chem. Lett. 1999, 1283

5d TMSOTf: Kurihara M. Hakamata W. J. Org. Chem. 2003, 68: 3413

6a Rh(III) triphos moieties: Ott J. Tombo GMR. Schmid B. Venanzi LM. Wang G. Ward TR. Tetrahedron Lett. 1989, 30: 6151

6b BF₃×Et₂O: Torok DS. Figueroa JJ. Scott WJ. J. Org. Chem. 1993, 58: 7274

6c Ti(OR)₄/TiCl₄: Mahrwald R. J. Prakt. Chem. 1994, 336: 361

6d Envirocat®: Beregszászi T. Molnár A. Synth. Commun. 1997, 27: 3705

6e Pt-Mo/ZrO₂: Reddy BM. Reddy VR. Giridhar D. Synth. Commun. 2001, 31: 1819

6f Microwave irradiation: Pério B. Dozias M.-J. Jacquault P. Hamelin J. Tetrahedron Lett. 1997, 38: 7867

7a Barbasiewicz M. Makosza M. Org. Lett. 2006, 8: 3745

7b Clerici A. Pastori N. Porta O. Tetrahedron 1998, 54: 15679

7c Perlmutter P. Puniani E. Tetrahedron Lett. 1996, 37: 3755

7d Dehmlow EV. Schmidt J. Tetrahedron Lett. 1976, 95

8

Most bismuth(III) compounds have an LD₅₀ value that is comparable to or even less than that of NaCl (see ref. 9d).

9a In Dangerous Properties of Industrial Materials Irwing-Sax N. Bewis RJ. Van Nostrand Reinhold; New York: 1989. p.283-284

9b In Dangerous Properties of Industrial Materials Irwing-Sax N. Bewis RJ. Van Nostrand Reinhold; New York: 1989. p.522-523

9c Dill K. McGown EL. In The Chemistry of Organic Arsenic, Antimony and Bismuth Compounds Patai S. Wiley; New York: 1994. p.695-713

9d Worsmer U. Nir I. In The Chemistry of Organic Arsenic, Antimony and Bismuth Compounds Patai S. Wiley; New York: 1994. p.715-723

9e In Chemistry of Arsenic, Antimony and Bismuth Reglinski J. Norman NC. Blackie Academic and Professional; New York: 1998. p.403-440

For reviews, see:

10a Marshall JA. Chemtracts: Org. Chem. 1997, 10: 1064

10b Suzuki H. Ikegami T. Matano Y. Synthesis 1997, 249

10c Organobismuth Chemistry Suzuki H. Matano Y. Elsevier; Amsterdam: 2001.

10d Leonard NM. Wieland LC. Mohan RS. Tetrahedron 2002, 58: 8373

10e Gaspard-Iloughmane H. Le Roux C. Eur. J. Org. Chem. 2004, 2517

10f Ollevier T. Desyroy V. Nadeau E. ARKIVOC 2007, (x): 10

11 Leonard NM. Oswald MC. Freiberg DA. Nattier BA. Smith RC. Mohan RS. J. Org. Chem. 2002, 67: 5202

12 Noyori and co-workers have reported the use of TMSOTf as a catalyst for the dioxolanation of ketones using 1,2-bis(trimethylsilyloxy)ethane under aprotic conditions in CH₂Cl₂: Tsunoda T. Suzuki M. Noyori R. Tetrahedron Lett. 1980, 21: 1357

13 The 1,3-dioxolanation of α,β-unsaturated aldehydes with 1,2-bis(trimethylsilyloxy)ethane and trimethylsilyl trifluoromethanesulfonate has also been reported: Hwu JR. Leu LC. Robl JA. Anderson DA. Wetzel JM.
J. Org. Chem. 1987, 52: 188

14 Bhosale RS. Bhosale SV. Bhosale SV. Solanke KS. Pawar RP. Chougule HS. Dongare MK. Synth. Commun. 2006, 36: 659

15 Arterburn JB. Perry MC. Org. Lett. 1999, 1: 769

16 Chen C.-T. Weng S.-S. Kao J.-Q. Lin C.-C. Jan M.-D. Org. Lett. 2005, 7: 3343

17 Ziyaei-Halimjani A. Azizi N. Saidi MR. J. Sci. Ind. Res. Iran 2005, 16: 37

18 Banik BK. Chapa M. Marquez J. Cardona M. Tetrahedron Lett. 2005, 46: 2341

19 Taskinen E. Struct. Chem. 2002, 13: 53

20 Langer SH. Connell S. Wender I. J. Org. Chem. 1958, 23: 50

21 Firouzabadi H. Iranpoor N. Hazarkhani H. Phosphorus, Sulfur Silicon Relat. Elem. 2002, 177: 2847

22 Len C. Pilard S. Lipka E. Vaccher C. Dubois M.-P. Shrinska Y. Tran V. Rabiller C. Tetrahedron 2005, 61: 10583

23 Karimi B. Rajabi J. Mol. Catal. A: Chem. 2005, 226: 165

24 Gopinath R. Haque SkJ. Patel BK. J. Org. Chem. 2002, 67: 5842

25 Stowell JC. Keith DR. Synthesis 1979, 132

26 Karimi B. Ebrahimian GR. Seradj H. Org. Lett. 1999, 1: 1737

27 Rondestvedt CS. J. Org. Chem. 1961, 26: 2247

28 Osuka A. Yamada H. Maruyama K. Mataga N. Asahi T. Ohkouchi M. Okada T. Yamazaki I. Nishimura Y.
J. Am. Chem. Soc. 1993, 115: 9439

29 Langille NF. Dakin LA. Panek JS. Org. Lett. 2003, 5: 575

30 Nasveschuk CG. Frein JD. Jui NT. Rovis T. Org. Lett. 2007, 9: 5099

31 For example, see: Matsushita Y.-I. Sugamoto K. Matsui T. Tetrahedron Lett. 2004, 45: 4723