Organocatalysis of the Morita-Baylis-Hillman Alkylation Using ­Trialkylphosphines

Marie E. Krafft; Kimberly A. Seibert

doi:10.1055/s-2006-951531

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2006(19): 3334-3336
DOI: 10.1055/s-2006-951531

LETTER

Organocatalysis of the Morita-Baylis-Hillman Alkylation Using Trialkylphosphines

Marie E. Krafft*, Kimberly A. Seibert
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USA
Fax: +1(850)6447409; e-Mail: mek@chem.fsu.edu;

Further Information

Publication History

Received 27 June 2006
Publication Date:
23 November 2006 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

Using a catalytic amount of trialkylphosphines, alkyl halides undergo efficient intramolecular Morita-Baylis-Hillman cyclization.

Key words

alkylation - cyclization - cycloalkenone - organocatalysis - ring closure

References and Notes

1a Dalko PI. Moisan L. Angew. Chem. Int. Ed. 2004, 43: 5138

Crossref Google Scholar
1b Saeyad J. List B. Org. Biomol. Chem. 2005, 3: 719

Crossref Google Scholar
1c Asymmetric Organocatalysis Berkessel A. Gröger H. Wiley-VCH; Weinheim: 2005.

Crossref Google Scholar
1d Ramachary DB. Barbas CF. Chem. Eur. J. 2004, 10: 5323

Crossref Google Scholar
1e List B. Tetrahedron 2002, 58: 5573

Crossref Google Scholar
2 Maryanoff BE. Rietz AB. Chem. Rev. 1989, 89: 863

Crossref Google Scholar
3a Alcaide B. Almendros P. Eur. J. Org. Chem. 2002, 1595

Crossref PubMed Google Scholar
3b Saito S. Yamamoto H. Acc. Chem. Res. 2004, 37: 570

Crossref PubMed Google Scholar
3c Palomo C. Oiarbide M. Garcia JM. Chem. Soc. Rev. 2004, 33: 65

Crossref PubMed Google Scholar
4a Brown SP. Goodwin NC. MacMillan DWC. J. Am. Chem. Soc. 2003, 125: 1192

Crossref Google Scholar
4b Paras NA. MacMillan DWC. J. Am. Chem. Soc. 2002, 124: 7894

Crossref Google Scholar
4c Berner OM. Tedeshi L. Enders D. Eur. J. Org. Chem. 2002, 1877

Crossref Google Scholar
5a Kerr MS. de Alaniz JR. Rovis T. J. Am. Chem. Soc. 2002, 124: 10298

Crossref PubMed Google Scholar
5b Kerr MS. Rovis T. J. Am. Chem. Soc. 2004, 126: 8876

Crossref PubMed Google Scholar
6a Appukkuttan P. Dehain W. Van der Eycken E. Eur. J. Org. Chem. 2003, 4713

Crossref PubMed Google Scholar
6b Leadbeater NE. Marco M. Tominack BJ. Org. Lett. 2003, 5: 3919

Crossref PubMed Google Scholar
7 Ma D. Cai Q. Synthesis 2004, 128

Article in Thieme Connect Google Scholar
8 Okino T. Nakamura S. Furukawa T. Takemoto Y. Org. Lett. 2004, 6: 625

Crossref PubMed Google Scholar
9 Roush WR. Methot JL. Adv. Synth. Catal. 2004, 346: 1035

Crossref Google Scholar
10a Krafft ME. Seibert KA. Haxell TFN. Chem. Commun. 2005, 5772

Crossref Google Scholar
10b Krafft ME. Haxell TFN. Seibert KA. Abboud KA. J. Am. Chem. Soc. 2006, 128: 4174

Crossref Google Scholar

11

General Procedure: To the halide in a 0.5 M solution of t-BuOH-CH₂Cl₂ (1:1), were added a 0.2 M KOH solution (1 equiv) and BnEt₃NCl (10 mol%). The reaction mixture was then treated with tributylphosphine (20 mol%) and allowed to stir at ambient temperature until the reaction was complete (TLC analysis). For entries 1, 4 and 5 (Table [2] ), a 1.0 M solution of t-BuOH-CH₂Cl₂ (1:1) was employed for the catalytic reaction.

12

For characterization data of compounds 1-6, 9, 12-16, 19, and 22, see ref. 10a. Bromide 7: ¹H NMR (500 MHz, CDCl₃): δ = 8.45 (m, 1 H, aromatic), 8.02 (m, 1 H, aromatic), 7.98 (m, 1 H, aromatic), 7.90 (m, 2 H, aromatic), 7.56 (m, 2 H, aromatic), 7.12 (td, J = 6.0, 15.45 Hz, 1 H, CH=CHCH₂), 7.07 (d, J = 15.45 Hz, 1 H, CH=CHCH₂), 3.46 (t, J = 6.6 Hz, 2 H, BrCH ₂CH₂), 2.41 (dt, J = 6.0, 7.3 Hz, 2 H, CH=CHCH ₂), 1.97 (tt, J = 6.6, 7.5 Hz, 2 H, CH ₂CH₂Br), 1.74 (tt, J = 7.3, 7.5 Hz, 2 H, CH=CH CH₂CH ₂). ¹³C NMR (75 MHz, CDCl₃): δ = 190.3, 148.5, 135.3, 135.1, 132.4, 129.9, 129.4, 128.4, 128.3, 127.7, 126.7, 126.2, 124.4, 32.3, 32.1, 31.8, 26.6. HRMS (FAB+): m/z [M + Na] calcd for C₁₇H₁₇OBrNa: 339.0368; found: 339.0360. FTIR (neat): 2934, 1691, 1665, 1615, 1460, 1295 cm^-1. Anal. Calcd for C₁₇H₁₇OBr: C, 64.37; H, 5.40. Found: C, 64.44; H, 5.46. Bromide 8: ¹H NMR (500 MHz, CDCl₃): δ = 8.32 (m, 2 H, aromatic), 8.05 (m, 2 H, aromatic), 7.10 (td, J = 6.8, 15.4 Hz, 1 H, CH=CHCH₂), 6.89 (td, J = 1.5, 15.4 Hz, 1 H, CH=CCH₂), 3.44 (t, J = 6.6 Hz, 2 H, CH ₂Br), 2.40 (ddt, J = 1.5, 6.6, 7.2 Hz, 2 H, C=CHCH ₂), 1.94 (tt, J = 6.6, 7.2 Hz, 2 H, CH ₂CH₂Br), 1.73 (tt, J = 7.2, 7.2 Hz, 2 H, C=CHCH ₂CH₂). ¹³C NMR (75 MHz, CDCl₃): δ = 188.8, 150.8, 149.7, 142.4, 129.4, 129.2, 125.6, 123.6, 123.5, 33.1, 31.9, 31.7, 26.3. HRMS (FAB+): m/z [M + H⁺] calcd for C₁₃H₁₅O₃NBr: 312.0237; found: 312.0235. FTIR (neat): 3106, 2937, 2861, 1673, 1620, 1601, 1523, 1344 cm^-1. Anal. Calcd for C₁₃H₁₄O₃NBr: C, 50.02; H, 4.52. Found: C, 50.05; H, 4.67. Bromide 10: ¹H NMR (500 MHz, CDCl₃): δ = 8.45 (m, 1 H, aromatic), 8.03 (m, 1 H, aromatic), 7.98 (m, 1 H, aromatic), 7.90 (m, 2 H, aromatic), 7.58 (m, 2 H, aromatic), 7.14 (d, J = 15.38 Hz, 1 H, CH=CHCH₂), 7.07 (td, J = 6.6, 15.4 Hz, 1 H, CH=CHCH₂), 3.49 (t, J = 6.6 Hz, 2 H, BrCH ₂CH₂), 2.56 (dt, J = 6.6, 7.3 Hz, 2 H, CH=CHCH ₂), 2.13 (tt, J = 6.6, 7.3 Hz, 2 H, CH ₂CH₂Br). ¹³C NMR (75 MHz, CDCl₃): δ = 189.8, 146.8, 135.2, 134.8, 132.3, 129.8, 129.3, 128.3, 128.2, 127.6, 126.6, 126.5, 124.2, 32.7, 30.9, 30.7. FTIR (neat): 3055, 2930, 1665, 1617, 1291 cm^-1. Anal. Calcd for C₁₆H₁₅OBr: C, 63.38; H, 4.99. Found: C, 63.39; H, 4.93.
Enone 11: ¹H NMR (500 MHz, CDCl₃): δ = 8.32 (m, 2 H, aromatic), 8.05 (m, 2 H, aromatic), 7.08 (td, J = 7.1, 15.4 Hz, 1 H, CH=CHCH₂), 6.93 (td, J = 1.5, 15.4 Hz, 1 H, CH=CHCH₂), 3.46 (t, J = 7.0 Hz, 2 H, CH ₂Br), 2.55 (dtd, J = 1.5, 7.0, 7.1 Hz, 2 H, CH=CHCH ₂), 2.11 (tt, J = 7.0, 7.0 Hz, 2 H, CH ₂CH₂Br). ¹³C NMR (75 MHz, CDCl₃): δ = 188.8, 149.9, 149.4, 142.4, 129.3, 126.3, 123.7, 35.5, 31.0, 30.6. FTIR (neat): 2936, 2854, 1674, 1622, 1602, 1436, 1248, 1028 cm^-1. Anal. Calcd for C₁₂H₁₂O₃NBr: C, 48.34; H, 4.06; N, 4.70. Found: C, 48.67; H, 4.34; N, 4.75. Enone 17: ¹H NMR (500 MHz, CDCl₃): δ = 8.12 (m, 1 H, aromatic), 7.92 (m, 1 H, aromatic), 7.87 (m, 2 H, aromatic), 7.75 (m, 1 H, aromatic), 7.55 (m, 2 H, aromatic), 6.64 (tt, J = 2.0, 7.3 Hz, 1 H, C=CHCH₂), 2.49 (dtt, J = 2.0, 2.4, 6.1 Hz, 2 H, CH=CHCH ₂), 2.30 (ttd, J = 2.4, 6.1, 7.2 Hz, 2 H, CH ₂CH=C), 1.78 (tt, J = 6.1, 6.1 Hz, 2 H, C=CH₂CH ₂), 1.71 (tt, J = 6.1, 6.1 Hz, 2 H, C=CHCH₂CH ₂). FTIR (neat): 2918, 2849, 1638, 1465, 1282 cm^-1. Anal. Calcd for C₁₇H₁₆O: C, 86.40; H, 6.82. Found: C, 86.10; H, 6.43. Enone 18: ¹H NMR (500 MHz, CDCl₃): δ = 8.27 (m, 2 H, aromatic), 7.73 (m, 2 H, aromatic), 6.57 (tt, J = 2.0, 7.4 Hz, 1 H, C=CHCH₂), 2.43 (dtt, J = 2.0, 2.4, 6.2 Hz, 2 H, CH=CCH ₂), 2.30 (ttd, J = 2.4, 6.2, 7.6 Hz, 2 H, C=CHCH ₂), 1.75 (tt, J = 6.2, 6.2 Hz, 2 H, C=CHCH₂CH ₂), 1.69 (tt, J = 6.2, 6.2 Hz, 2 H, C=CHCH₂CH₂CH ₂). ¹³C NMR (75 MHz, CDCl₃): δ = 195.9, 149.0, 146.5, 144.4, 138.6, 129.6, 123.2, 26.2, 23.4, 21.7, 21.4. HRMS (EI+): m/z calcd for C₁₃H₁₃O₃N: 231.08948; found: 231.08955. FTIR (neat): 2933, 1648, 1301, 1522, 1350 cm^-1. Anal. Calcd for C₁₃H₁₃O₃N: C, 67.52; H, 5.67. Found: C, 67.30; H, 5.74.
Enone 20: ¹H NMR (500 MHz, CDCl₃): δ = 8.25 (m, 1 H, aromatic), 7.83-7.94 (m, 4 H, aromatic), 7.52-7.59 (m, 2 H, aromatic), 6.61 (tt, J = 1.7, 2.5 Hz, 1 H, C=CHCH₂), 2.81 (dtt, J = 1.7, 2.2, 7.5 Hz, 2 H, CH=CCH ₂), 2.67 (tdt, J = 2.2, 2.5, 7.5 Hz, 2 H, CH ₂CH=C), 2.06 (tt, J = 7.5, 7.5 Hz, 2 H, CH ₂CH₂CH=C). ¹³C NMR (75 MHz, CDCl₃): δ = 194.1, 146.7, 144.6, 136.1, 134.9, 132.2, 129.9, 129.1, 128.0, 127.8, 127.7, 126.5, 125.1, 34.3, 32.0, 22.7. HRMS (FAB+): m/z [M + Na] calcd for C₁₆H₁₄ONa: 245.0948; found: 245.0942. FTIR (neat): 2952, 1636, 1355, 1299 cm^-1. Anal. Calcd for C₁₆H₁₄O: C, 86.45; H, 6.35. Found: C, 86.41; H, 6.33. Enone 21: ¹H NMR (500 MHz, CDCl₃): δ = 8.28 (m, 2 H, aromatic), 7.84 (m, 2 H, aromatic), 6.57 (tt, J = 2.0, 12.4 Hz, 1 H, C=CHCH₂), 2.76 (dtt, J = 2.4, 7.6, 12.4 Hz, 2 H, CH=CCH ₂), 2.66 (tdt, J = 2.0, 2.4, 7.6 Hz, 2 H, C=CHCH ₂), 2.04 (tt, J = 7.6, 7.6 Hz, 2 H, C=CHCH₂CH ₂). ¹³C NMR (75 MHz, CDCl₃): δ = 192.0, 149.5, 149.1, 144.5, 144.3, 129.5, 123.4, 34.6, 31.5, 22.7. HRMS (EI+): m/z [M + Na] calcd for C₁₂H₁₁O₃N: 217.07378; found: 217.07390. FTIR (neat): 2957, 2871, 1646, 1601, 1522, 1348 cm^-1. Anal. Calcd for C₁₂H₁₁O₃N: C, 66.35; H, 5.10. Found: C, 66.21; H, 5.10.