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Synthesis 2010(16): 2771-2775  
DOI: 10.1055/s-0030-1258148
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

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;
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Publication History

Received 8 March 2010
Publication Date:
02 July 2010 (online)

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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

    References

  • 1a Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   3rd ed.:  Wiley; New York: 1999. 
    Google Scholar
  • 1b Hanson JR. Protecting Groups in Organic Synthesis   Blackwell; Malden / MA: 1999. 
    Google Scholar
  • 1c Kocienski PJ. Protecting Groups   Georg Thieme Verlag; Stuttgart: 1994. 
    Google Scholar
  • 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.
    Google Scholar
  • 1e Schnitz E. Eichorn I. In The Chemistry of the Ether Linkage   Patai S. Wiley; New York: 1967.  Chap. 7.
    Google Scholar
  • 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 
    Google Scholar
  • For other examples of acetal allylation, see:
  • 2b Bartlett PA. Johnson WS. Elliott JD. J. Am. Chem. Soc.  1983,  105:  2088 
    Google Scholar
  • 2c Denmark SE. Almstead NG. J. Org. Chem.  1991,  56:  6458 
    Google Scholar
  • 2d Denmark SE. Almstead NG. J. Org. Chem.  1991,  56:  6485 
    Google Scholar
  • 2e Egami Y. Takayanagi M. Tanino K. Kuwajima I. Heterocycles  2000,  52:  583 
    Google Scholar
  • 2f Morelli C. Durì L. Saladino A. Speranza G. Manitto P. Synthesis  2004,  3005 
    Google Scholar
  • 2g Jiang S. Agoston GE. Chen T. Cabal M.-P. Turos E. Organometallics  1995,  14:  4697 
    Google Scholar
  • 2h Hunter R. Michael JP. Tomlinson GD. Tetrahedron  1994,  50:  871 
    Google Scholar
  • 2i Carrel F. Giraud S. Spertini O. Vogel P. Helv. Chim. Acta  2004,  87:  1048 
    Google Scholar
  • 2j Suzuki T. Oriyama T. Synth. Commun.  1999,  29:  1263 
    Google Scholar
  • 3a Daignault RA. Eliel EL. Org. Synth. Collect. Vol. V   Wiley; New York: 1973.  p.303 
    Google Scholar
  • 3b Caserio FF. Roberts JD. J. Am. Chem. Soc.  1958,  80:  5837 
    Google Scholar
  • 3c Fieser LF. Stevenson R. J. Am. Chem. Soc.  1954,  76:  1728 
    Google Scholar
  • 3d Howard EG. Lindsey RV. J. Am. Chem. Soc.  1960,  82:  158 
    Google Scholar
  • 3e Dauben WG. Gerdes JM. Look GC. J. Org. Chem.  1986,  51:  4964 
    Google Scholar
  • For some recent examples, see:
  • 4a DeAngelis A. Panne P. Yap GPA. Fox JM. J. Org. Chem.  2008,  73:  1435 
    Google Scholar
  • 4b TsOH-SiO2: Borah KJ. Phukan M. Borah R. Synth. Commun.  2008,  38:  3082 
    Google Scholar
  • 4c La(NO3)3×6H2O: Srinivasulu N. Suryakiran N. Rajesh K. Reddy SM. Venkateswarlu Y. Synth. Commun.  2008,  38:  1753 
    Google Scholar
  • 4d H3PW12O40: Yang S. Zhang Y. Du X. Merle PG. Rare Met.  2008,  27:  89 
    Google Scholar
  • 4e TfOH and formalin: Du Y. Tian F. Catal. Commun.  2007,  8:  2012 
    Google Scholar
  • 4f Polystyrenesulfonic acid: Polshettiwar V. Varma RS. J. Org. Chem.  2007,  72:  7420 
    Google Scholar
  • 4g Ammonium triflate: Karimi B. Ghoreishi-Nezhad M. J. Mol. Catal. A: Chem.  2007,  277:  262 
    Google Scholar
  • 4h Ce(OTf)3: Ono F. Takenaka H. Fujikawa T. Mori M. Sato TJ. Synthesis  2009,  1318 
    Google Scholar
  • 5a Ethylene glycol/TMSCl: Chan TH. Brook MA. Chaly T. Synthesis  1983,  203 
    Google Scholar
  • 5b AlPO4: Bautista FM. Campelo JM. García A. Leon J. Luna D. Marinas JM. J. Prakt. Chem.  1994,  336:  620 
    Google Scholar
  • 5c CdI2: Laskar DD. Prajapati D. Sandhu JS. Chem. Lett.  1999,  1283 
    Google Scholar
  • 5d TMSOTf: Kurihara M. Hakamata W. J. Org. Chem.  2003,  68:  3413 
    Google Scholar
  • 6a Rh(III) triphos moieties: Ott J. Tombo GMR. Schmid B. Venanzi LM. Wang G. Ward TR. Tetrahedron Lett.  1989,  30:  6151 
    Google Scholar
  • 6b BF3×Et2O: Torok DS. Figueroa JJ. Scott WJ. J. Org. Chem.  1993,  58:  7274 
    Google Scholar
  • 6c Ti(OR)4/TiCl4: Mahrwald R. J. Prakt. Chem.  1994,  336:  361 
    Google Scholar
  • 6d Envirocat®: Beregszászi T. Molnár A. Synth. Commun.  1997,  27:  3705 
    Google Scholar
  • 6e Pt-Mo/ZrO2: Reddy BM. Reddy VR. Giridhar D. Synth. Commun.  2001,  31:  1819 
    Google Scholar
  • 6f Microwave irradiation: Pério B. Dozias M.-J. Jacquault P. Hamelin J. Tetrahedron Lett.  1997,  38:  7867 
    Google Scholar
  • 7a Barbasiewicz M. Makosza M. Org. Lett.  2006,  8:  3745 
    Google Scholar
  • 7b Clerici A. Pastori N. Porta O. Tetrahedron  1998,  54:  15679 
    Google Scholar
  • 7c Perlmutter P. Puniani E. Tetrahedron Lett.  1996,  37:  3755 
    Google Scholar
  • 7d Dehmlow EV. Schmidt J. Tetrahedron Lett.  1976,  95 
    Google Scholar
  • 9a In Dangerous Properties of Industrial Materials   Irwing-Sax N. Bewis RJ. Van Nostrand Reinhold; New York: 1989.  p.283-284  
    Google Scholar
  • 9b In Dangerous Properties of Industrial Materials   Irwing-Sax N. Bewis RJ. Van Nostrand Reinhold; New York: 1989.  p.522-523  
    Google Scholar
  • 9c Dill K. McGown EL. In The Chemistry of Organic Arsenic, Antimony and Bismuth Compounds   Patai S. Wiley; New York: 1994.  p.695-713  
    Google Scholar
  • 9d Worsmer U. Nir I. In The Chemistry of Organic Arsenic, Antimony and Bismuth Compounds   Patai S. Wiley; New York: 1994.  p.715-723  
    Google Scholar
  • 9e In Chemistry of Arsenic, Antimony and Bismuth   Reglinski J. Norman NC. Blackie Academic and Professional; New York: 1998.  p.403-440  
    Google Scholar
  • For reviews, see:
  • 10a Marshall JA. Chemtracts: Org. Chem.  1997,  10:  1064 
    Google Scholar
  • 10b Suzuki H. Ikegami T. Matano Y. Synthesis  1997,  249 
    Google Scholar
  • 10c Organobismuth Chemistry   Suzuki H. Matano Y. Elsevier; Amsterdam: 2001. 
    Google Scholar
  • 10d Leonard NM. Wieland LC. Mohan RS. Tetrahedron  2002,  58:  8373 
    Google Scholar
  • 10e Gaspard-Iloughmane H. Le Roux C. Eur. J. Org. Chem.  2004,  2517 
    Google Scholar
  • 10f Ollevier T. Desyroy V. Nadeau E. ARKIVOC  2007,  (x):  10 
    Google Scholar
  • 11 Leonard NM. Oswald MC. Freiberg DA. Nattier BA. Smith RC. Mohan RS. J. Org. Chem.  2002,  67:  5202 
    CrossrefGoogle Scholar
  • 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 
    CrossrefGoogle Scholar
  • 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 
    CrossrefGoogle Scholar
  • 14 Bhosale RS. Bhosale SV. Bhosale SV. Solanke KS. Pawar RP. Chougule HS. Dongare MK. Synth. Commun.  2006,  36:  659 
    CrossrefGoogle Scholar
  • 15 Arterburn JB. Perry MC. Org. Lett.  1999,  1:  769 
    CrossrefGoogle Scholar
  • 16 Chen C.-T. Weng S.-S. Kao J.-Q. Lin C.-C. Jan M.-D. Org. Lett.  2005,  7:  3343 
    CrossrefGoogle Scholar
  • 17 Ziyaei-Halimjani A. Azizi N. Saidi MR. J. Sci. Ind. Res. Iran  2005,  16:  37 
    Google Scholar
  • 18 Banik BK. Chapa M. Marquez J. Cardona M. Tetrahedron Lett.  2005,  46:  2341 
    CrossrefGoogle Scholar
  • 19 Taskinen E. Struct. Chem.  2002,  13:  53 
    CrossrefGoogle Scholar
  • 20 Langer SH. Connell S. Wender I. J. Org. Chem.  1958,  23:  50 
    CrossrefGoogle Scholar
  • 21 Firouzabadi H. Iranpoor N. Hazarkhani H. Phosphorus, Sulfur Silicon Relat. Elem.  2002,  177:  2847 
    CrossrefGoogle Scholar
  • 22 Len C. Pilard S. Lipka E. Vaccher C. Dubois M.-P. Shrinska Y. Tran V. Rabiller C. Tetrahedron  2005,  61:  10583 
    CrossrefGoogle Scholar
  • 23 Karimi B. Rajabi J. Mol. Catal. A: Chem.  2005,  226:  165 
    CrossrefGoogle Scholar
  • 24 Gopinath R. Haque SkJ. Patel BK. J. Org. Chem.  2002,  67:  5842 
    Google Scholar
  • 25 Stowell JC. Keith DR. Synthesis  1979,  132 
    Article in Thieme ConnectGoogle Scholar
  • 26 Karimi B. Ebrahimian GR. Seradj H. Org. Lett.  1999,  1:  1737 
    CrossrefGoogle Scholar
  • 27 Rondestvedt CS. J. Org. Chem.  1961,  26:  2247 
    CrossrefGoogle Scholar
  • 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 
    CrossrefGoogle Scholar
  • 29 Langille NF. Dakin LA. Panek JS. Org. Lett.  2003,  5:  575 
    CrossrefGoogle Scholar
  • 30 Nasveschuk CG. Frein JD. Jui NT. Rovis T. Org. Lett.  2007,  9:  5099 
    CrossrefGoogle Scholar
  • 31 For example, see: Matsushita Y.-I. Sugamoto K. Matsui T. Tetrahedron Lett.  2004,  45:  4723 
    CrossrefGoogle Scholar
8

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