Synthesis of α,β-Unsaturated
Ketones by Rhodium-Catalyzed Carbonylative Arylation of Internal
Alkynes with Arylboronic Acids

Melih Kuş; Özge Aksin Artok; Firat Ziyanak; Levent Artok

doi:10.1055/s-2008-1078047

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 2008(17): 2587-2592
DOI: 10.1055/s-2008-1078047

LETTER

Synthesis of α,β-Unsaturated Ketones by Rhodium-Catalyzed Carbonylative Arylation of Internal Alkynes with Arylboronic Acids

Melih Kuş, Özge Aksin Artok, Firat Ziyanak, Levent Artok*
Department of Chemistry, Faculty of Science, Izmir Institute of Technology, Urla 35430, Izmir, Turkey
Fax: +90(232)7507509; e-Mail: leventartok@iyte.edu.tr;

Further Information

Publication History

Received 5 June 2008
Publication Date:
10 September 2008 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

The Rh-catalyzed reaction of arylboronic acids with internal alkynes under a CO atmosphere in the presence of an acid additive afforded α,β-unsaturated ketones as the major products. Hydroacylation of internal alkynes, except in the case of diaryl acetylenes, proceeded in syn fashion, yielding the E-configured isomer. A mixture of E- and Z-isomers was obtained with diphenyl acetylene. Reactions were also highly regioselective for various nonsymmetric alkynes.

Key words

carbonylation - boron - rhodium - enones - alkynes

References and Notes

1 Aksin Ö. Dege N. Artok L. Türkmen H. Çetinkaya B. Chem. Commun. 2006, 3187

Crossref Google Scholar
2a Sauthier M. Castanet Y. Mortreux A. Chem. Commun. 2004, 1520

Google Scholar
2b Chochois H. Sauthier M. Maerten E. Castanet Y. Mortreux A. Tetrahedron 2006, 62: 11740

Google Scholar
2c Menard F. Weise CF. Lautens M. Org. Lett. 2007, 9: 5335

Google Scholar
2d Dheur J. Sauthier M. Castanet Y. Mortreux A. Adv. Synth. Catal. 2007, 349: 2499

Google Scholar
3a Willis MC. Randell-Sly HE. Woodward RL. Steven J. McNally SJ. Currie GS. J. Org. Chem. 2006, 71: 5291

Google Scholar
3b Tanaka K. Shibata Y. Suda T. Hagiwara Y. Hirano M. Org. Lett. 2007, 9: 1215

Google Scholar
3c Imai M. Tanaka M. Tanaka K. Yamamoto Y. Imai-Ogata N. Shimowatari M. Nagumo S. Kawahara N. Suemune H. J. Org. Chem. 2004, 69: 1144

Google Scholar
3d Jun C.-H. Lee H. Hong J.-B. Kwon BI. Angew. Chem. Int. Ed. 2002, 41: 2146

Google Scholar
3e Moxham GL. Randell-Sly HE. Brayshaw SK. Woodward RL. Weller AS. Willis MC. Angew. Chem. Int. Ed. 2006, 45: 7618

Google Scholar
3f Tanaka K. Tanaka M. Suemune H. Tetrahedron Lett. 2005, 46: 6053

Google Scholar
3g Willis MC. Sapmaz S. Chem. Commun. 2001, 2558

Google Scholar
3h Jun C.-H. Jo E.-A. Park J.-W. Eur. J. Org. Chem. 2007, 1869

Google Scholar
3i Stemmlera RT. Bolma C. Adv. Synth. Catal. 2007, 349: 1185

Google Scholar
3j Imai M. Tanaka M. Nagumo S. Kawahara N. Suemune H. J. Org. Chem. 2007, 72: 2543

Google Scholar
3k Rueda XY. Castillón S. J. Organomet. Chem. 2007, 692: 1628

Google Scholar
3l Lochow CF. Miller RG. J. Am. Chem. Soc. 1976, 98: 1281

Google Scholar
3m Kokubo K. Matsumasa K. Miura M. Nomura M. J. Org. Chem. 1997, 62: 4564

Google Scholar
3n Miura M. Nomura M. J. Synth. Org. Chem. Jpn. 2000, 58: 578

Google Scholar
3o Kokubo K. Matsumasa K. Nishinaka Y. Miura M. Nomura M. Bull. Chem. Soc. Jpn. 1999, 72: 303

Google Scholar
3p Marder TD. Roe DC. Milstein D. Organometallics 1988, 7: 1451

Google Scholar
Other acylation reagents used:
4a Hydrogenative aroylation with an anhydride: Hong Y.-T. Barchuk A. Krische MJ. Angew. Chem. Int. Ed. 2006, 45: 6885

Google Scholar
4b Hydroacylation of ethylene with acyl halides: Schwartz J. Cannon JB. J. Am. Chem. Soc. 1974, 96: 4721

Google Scholar
Other metal catalysis - Ir catalyzed:
5a Nishinaka Y. Satoh T. Miura M. Morisaka H. Nomura M. Matsui H. Yamaguchi C. Bull. Chem. Soc. Jpn. 2001, 74: 1727

Google Scholar
Ni catalyzed:
5b Tsuda T. Kiyoi T. Saegusa T. J. Org. Chem. 1990, 55: 2555

Google Scholar
Ru catalyzed:
5c Kondo T. Tsuji Y. Watanabe Y. Tetrahedron Lett. 1987, 28: 6229

Google Scholar
5d Kondo T. Akazome M. Tsuji Y. Watanabe Y. J. Org. Chem. 1990, 55: 1286

Google Scholar
Co catalyzed:
5e Lenges CP. Brookhart M. J. Am. Chem. Soc. 1997, 119: 3165

Google Scholar
7a Duke PJ. Boykin DW. J. Org. Chem. 1972, 37: 1436

Google Scholar
7b Black WB. Lutz RE. J. Am. Chem. Soc. 1953, 75: 5990

Google Scholar
7c Mittal S. Durani S. Kapil RS. J. Med. Chem. 1985, 28: 492

Google Scholar
9 Hayashi T. Inoue K. Taniguchi N. Ogasawara M. J. Am. Chem. Soc. 2001, 123: 9918

Crossref PubMed Google Scholar
10 Rhodium(I)-catalyzed reaction of 2-bromo-substituted phenylboronic acids with alkynes under CO atmosphere leading to indenone structures was reported. See: Harada Y. Nakanishi J. Fujihara H. Tobisu M. Fukumoto Y. Chatani N. J. Am. Chem. Soc. 2007, 29: 5766

Google Scholar

6

Typical Conditions for the Synthesis of 3 A mixture of alkyne (1.5 mmol), arylboronic acid (3 mmol), [Rh(C₂H₄)₂Cl]₂ (3 mol% Rh), TFA (2 mmol), H₂O (0.1 mL) in MeOH (9.9 mL, predried) was added into a 50 mL stainless steel autoclave with a glass insert tube. Then, the sealed autoclave was evacuated, and purged with 10 atm CO twice, successively. Subsequently, the reactor was pressurized to 5 atm with CO and the mixture was stirred magnetically in a preheated oil bath. After cooling, the reaction mixture was recovered with EtOAc. The products were analyzed by GC and GC-MS and isolated by column chromatography. Purity of the products were >96% as determined by ^¹H NMR analyses.
( E , Z )-1,2,3-Triphenylprop-2-en-1-one (3aa)
Hexane-EtOAc.
Isomer (E)-3aa: white solid; mp 98.7-99.2 ˚C (lit.: 99-101 ˚C,^7a 103-103.5 ˚C,^7b 96.5-97.5 ˚C^7c). ^¹H NMR (400 MHz, CDCl₃): δ = 7.07-7.56 (m, 14 H), 7.86 (d, J = 7.2 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 126.4, 128.0, 128.2, 128.4, 128.7, 128.8, 128.9, 129.7, 130.1, 133.6, 135.4, 136.3, 138.0, 140.8, 199.4. MS (EI): m/z (%) = 284(93) [M⁺], 256(5), 206(9), 178(31), 105(100), 77(20). FTIR (ATR): ν = 1649 (CO) (lit.: 1661,^7a 1640^7c) cm^-¹. HRMS: m/z calcd [M⁺]: 284.1196; found: 284.1189.
Isomer (Z)-3aa: yellow solid; mp 78.0-84.1 ˚C (lit.: 85-87 ˚C,^7a 88-89 ˚C,^7b 82.5-83.5 ˚C^7c). ^¹H NMR (400 MHz, CDCl₃): δ = 7.10-7.50 (m, 14 H), 7.99 (d, J = 6.8 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 127.9, 128.2, 128.3, 128.8, 128.9, 129.7, 129.8, 130.3, 132.2, 134.8, 136.5, 138.2, 140.1, 140.8, 197.6. MS (EI): m/z (%) = 284 (87) [M⁺], 256 (7), 206 (20), 178 (47), 105 (100), 77 (83). FTIR (ATR):
ν = 1660 (CO) (lit.: 1671,^7a 1661^7c) cm^-¹. HRMS: m/z calcd [M⁺]: 284.1196; found: 284.1197.
( E , Z )-1-(4-Methoxyphenyl)-2,3-diphenylprop-2-en-1-one (3ab)
Hexane-benzene; hexane-CH₂Cl₂.
Isomer (E)-3ab: white solid; mp 81.1-84.3 (lit.: 84-84.3 ˚C^7c). ^¹H NMR (400 MHz, CDCl₃): δ = 3.85 (s, 3 H), 6.92 (d, J = 8.8 Hz, 2 H), 7.09-7.36 (m, 11 H), 7.90 (d, J = 8.8 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃: δ = 55.5, 113.6, 127.9, 128.2, 128.6, 128.8, 129.6, 130.2, 130.4, 132.3, 135.0, 136.8, 137.8, 141.0, 163.1, 196.3. MS (EI): m/z (%) = 314 (47) [M⁺], 197 (14), 178 (14), 135 (100), 107 (9), 92 (10), 77 (19). FTIR (ATR): ν = 1633 (CO) (lit.: 1640^7c) cm^-¹. HRMS: m/z calcd [M⁺]: 314.1301; found: 314.1294.
Isomer (Z)-3ab: pale yellow solid; mp 88.7-89.2 ˚C (lit.: 78-79 ˚C^7c). ^¹H NMR (400 MHz, CDCl₃): δ = 3.79 (s, 3 H), 6.83 (d, J = 8.8 Hz, 2 H), 7.12-7.48 (m, 11 H), 7.97 (d, J = 8.8 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 55.4, 114.0, 126.3, 127.9, 128.1, 128.4, 128.8, 129.4, 129.5, 132.1, 135.5, 138.2, 140.9, 164.0, 197.9. MS (EI): m/z (%) = 314 (58) [M⁺], 197 (18), 178 (19), 135 (100), 107 (12), 92 (13), 77 (23). FTIR (ATR): ν = 1657 (CO) (lit.: 1655^7c) cm^-¹. HRMS: m/z calcd [M⁺]: 314.1301; found: 314.1301.
( E , Z )-2,3-Diphenyl-1- p -tolylprop-2-en-1-one (3ac) Hexane-benzene.
Isomer (E)-3ac: white solid; mp 90.8-91.8 ˚C. ^¹H NMR (400 MHz, CDCl₃): δ = 2.41 (s, 3 H), 7.08-7.39 (m, 13 H), 7.79 (d, J = 8.0 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 21.6, 126.3, 127.9, 128.2, 128.8, 128.8, 129.0, 129.6, 130.1, 130.3, 134.9, 135.3, 136.7, 139.1, 140.9, 143.0, 197.5. MS (EI): m/z (%) = 298 (75) [M⁺], 283 (15), 205 (6), 181 (23), 178 (25), 119 (100), 91 (48). FTIR (ATR): ν = 1643 (CO) cm^-¹. HRMS: m/z calcd [M⁺]: 298.1352; 298.1346.
Isomer (Z)-3ac: pale yellow solid; mp 59.8-61.8 ˚C. ^¹H NMR (400 MHz, CDCl₃): δ = 2.32 (s, 3 H), 7.10-7.47 (m, 13 H), 7.89 (d, J = 8.4 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 21.7, 126.3, 128.0, 128.1, 128.5, 128.8, 129.5, 129.7, 129.9, 134.0, 135.5, 138.1, 141.0, 144.7, 199.0. MS (EI): m/z (%) = 298 (100) [M⁺], 283 (12), 182 (20), 119 (55), 91 (11). FTIR (ATR): ν = 1654 (CO) cm^-¹. HRMS: m/z calcd [M⁺]: 298.1352; found: 298.1341.
( E , Z )-2,3-Diphenyl-1- m -tolylprop-2-en-1-one (3ad)
Hexane-benzene.
Isomer (E)-3ad: further column chromatographed with hexane-EtOAc; white solid; mp 66.3-68.7 ˚C. ^¹H NMR (400 MHz, CDCl₃): δ = 2.40 (s, 3 H), 7.06-7.38 (m, 13 H), 7.64 (d, J = 7.6 Hz, 1 H), 7.68 (s, 1 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 21.4, 127.06, 127.9, 128.08, 128.2, 128.8, 128.9, 129.7, 130.2, 130.3, 132.9 134.9, 136.6, 138.2, 138.2, 140.0, 140.9, 197.9. MS (EI): m/z (%) = 298 (75) [M⁺], 283 (10), 181 (23), 178 (25), 119 (100), 91 (48). FTIR (ATR):
ν = 1635 (CO) cm^-¹. HRMS: m/z calcd [M⁺]: 298.1352; 298.1351.
Isomer (Z)-3ad: yellow oil. ^¹H NMR (400 MHz, CDCl₃):
δ = 2.32 (s, 3 H), 7.10-7.48 (m, 13 H), 7.65 (d, J = 8.0 Hz, 1 H), 7.83 (s, 1 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 21.3, 126.3, 127.3, 128.0, 128.1, 128.4, 128.6, 128.8, 129.9, 129.9, 134.5, 135.5, 136.3, 138.1, 138.5, 141.0, 199.5. MS (EI): m/z (%) = 298 (92) [M⁺], 283 (11), 181 (25), 178 (30), 119 (100), 91 (33). FTIR (ATR): ν = 1660 (CO) cm^-¹. HRMS: m/z calcd [M⁺]: 298.1352; found: 298.1359.
( E )-1-Phenyl-2-propylhex-2-en-1-one (3ba)
Hexane-EtOAc; pale yellow oil. ^¹H NMR (400 MHz, CDCl₃): δ = 0.94 (t, J = 7.4 Hz, 3 H), 0.96 (t, J = 7.4 Hz, 3 H), 1.41-1.52 (m, 4 H), 2.27 (q, J = 7.2 Hz, 2 H), 2.47 (t, J = 7.2 Hz, 2 H), 6.20 (t, J = 7.6 Hz, 1 H), 7.38-7.43 (m, 2 H), 7.47-7.52 (m, 1 H), 7.63-7.67 (m, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 14.0, 14.1, 22.2, 28.7, 30.9, 128.0, 129.3, 131.4, 139.1, 141.2, 145.7, 199.0. MS (EI): m/z (%) = 216 (100) [M⁺], 173 (7), 145 (9), 105 (27), 77 (5). FTIR (ATR): ν = 1647 (CO) cm^-¹. HRMS: m/z calcd [M⁺]: 216.1509; found: 216.1507.
( E )-1-(4-Methoxyphenyl)-2-propylhex-2-en-1-one (3bb) Hexane-EtOAc; pale yellow oil. ^¹H NMR (400 MHz, CDCl₃): δ = 0.91-0.98 (m, 6 H), 1.41-1.51 (m, 4 H), 2.26 (q, J = 7.2 Hz, 2 H), 2.46 (t, J = 7.6 Hz, 2 H), 3.86 (s, 3 H), 6.11 (t, J = 7.6 Hz, 1 H), 6.91 (d, J = 8.8 Hz, 2 H), 7.71 (d, J = 8.8 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 14.0, 14.1, 22.2, 22.3, 29.2, 30.7, 55.4, 113.3, 131.4, 131.8, 141.1, 143.1, 162.6, 198.0. MS (EI): m/z (%) = 246 (14) [M⁺], 203 (22), 175 (18), 135 (100), 107 (10), 92 (14), 77 (21). FTIR (ATR): ν = 1641 (CO) cm^-¹. HRMS: m/z calcd [M⁺]: 246.1614; found: 246.1603.
( E )-2-Propyl-1- p -tolylhex-2-en-1-one (3bc)
Hexane-EtOAc; pale yellow oil. ^¹H NMR (400 MHz, CDCl₃): δ = 0.94 (t, J = 7.6 Hz, 6 H), 1.46 (sext, J = 7.6 Hz, 4 H), 2.26 (q, J = 7.6 Hz, 2 H), 2.40 (s, 3 H), 2.46 (t, J = 8.0 Hz, 2 H), 6.16 (t, J = 7.4 Hz, 1 H), 7.21 (d, J = 8.0 Hz, 2 H), 7.59 (d, J = 8.0 Hz, 1 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 14.0, 14.1, 21.5, 22.2, 22.3, 28.9, 30.8, 128.7, 129.6, 136.2, 141.2, 142.1, 144.6, 198.8. MS (EI): m/z (%) = 230 (36) [M⁺], 215 (92), 201 (20), 187 (38), 173 (29), 159 (39), 145 (22), 119 (100), 91 (71). FTIR (ATR): ν = 1645 (CO)
cm^-¹. HRMS: m/z calcd [M⁺]: 230.1665; found: 230.1662.
( E )-Methyl 4-(4-Methoxyphenyl)-3-butyl-4-oxobut-2-enoate (3cb) Hexane-EtOAc; pale yellow oil. ^¹H NMR (400 MHz, CDCl₃): δ = 0.89 (t, J = 7.2 Hz, 3 H), 1.40-1.50 (m, 4 H), 2.98 (t, J = 7.6 Hz, 2 H), 3.76 (s, 3 H), 3.88 (s, 3 H), 5.99 (s, 1 H), 6.95 (d, J = 9.2 Hz, 2 H), 7.84 (d, J = 9.2 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 13.8, 22.9, 29.2, 30.5, 51.5, 55.5, 113.8, 122.0, 128.8, 132.2, 157.9, 163.9, 166.1, 196.5. MS (EI): m/z (%) = 276 (28) [M⁺], 245 (20), 217 (22), 135 (100). FTIR (ATR): ν = 1654 (CO), 1722 (COOMe) cm^-¹. HRMS: m/z calcd [M⁺]: 276.1356; found: 276.1355.
( E )-Methyl 4-(4-Methoxyphenyl)-3-methyl-4-oxobut-2-enoate (3db)
Hexane-EtOAc; pale yellow oil. ^¹H NMR (400 MHz, CDCl₃): δ = 2.42 (d, J = 1.6 Hz, 3 H), 3.77 (s, 3 H), 3.88 (s, 3 H), 6.09 (q, J = 1.6 Hz, 1 H), 6.95 (d, J = 9.2 Hz, 2 H), 7.83 (d, J = 8.8 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 16.0, 51.6, 55.5, 113.9, 123.0, 128.1, 132.2, 153.1, 163.9, 166.3, 196.5. MS (EI): m/z (%) = 234 (16) [M⁺], 203 (20), 135 (100), 107 (10), 92 (10), 77 (10), 62 (9). FTIR (ATR):
ν = 1651 (CO), 1720 (-COOCH₃) cm^-¹. HRMS: m/z calcd [M⁺]: 234.0887; found: 234.0884.
( E )-2-Methyl-1,3-diphenylprop-2-en-1-one (3ea)
Hexane-EtOAc; yellow oil. ^¹H NMR (400 MHz, CDCl₃):
δ = 2.27 (d, J = 1.6 Hz, 3 H), 7.18 (d, J = 1.6 Hz, 1 H), 7.30-7.56 (m, 8 H), 7.71-7.77 (m, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 14.4, 128.2, 128.5, 128.6, 129.5, 129.7, 131.7, 135.8, 136.9, 138.5, 142.2, 199.5. MS (EI): m/z (%) = 222 (100) [M⁺], 207 (33), 115 (32), 77 (48). FTIR (ATR): ν = 1642 (CO) cm^-¹. HRMS: m/z calcd [M⁺]: 222.1039; found: 222.1032.
( E )-1-(4-Methoxyphenyl)-2-methyl-3-phenylprop-2-en-1-one (3eb)
Hexane-EtOAc; yellow oil. ^¹H NMR (400 MHz, CDCl₃):
δ = 2.25 (d, J = 1.6 Hz, 3 H), 3.87 (s, 3 H), 6.95 (d, J = 9.2 Hz, 2 H), 7.10 (d, J = 1.6 Hz, 1 H), 7.30-7.43 (m, 5 H), 7.81 (d, J = 9.2 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 14.9, 55.5, 113.5, 128.3, 128.4, 129.6, 130.7, 132.0, 137.0, 140.0, 162.8, 198.3. MS (EI): m/z (%) = 252 (38) [M⁺], 135 (100), 145 (15), 115 (26). FTIR (ATR): ν = 1638 (CO) cm^-¹. HRMS: m/z calcd [M⁺]: 252.1145; found: 252.1138.
Compounds 3fb and 3fb′Hexane-EtOAc.
( E )-2-Benzylidene-1-(4-methoxyphenyl)pentan-1-one (3fb) Pale yellow oil. ^¹H NMR (400 MHz, CDCl₃): δ = 0.98 (t, J = 7.2 Hz, 3 H), 1.57 (sext, J = 7.6 Hz, 2 H), 2.71 (t, J = 7.8 Hz, 2 H), 3.89 (s, 3 H), 6.95 (d, J = 9.2 Hz, 2 H), 6.98 (s, 1 H), 7.30-7.42 (m, 5 H), 7.85 (d, J = 9.2 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 14.3, 22.0, 30.2, 55.5, 113.5, 128.1, 128.4, 129.1, 130.9, 132.1, 135.9, 138.5, 142.4, 163.0, 198.2. MS: (EI): m/z (%) = 280 (56) [M⁺], 251 (15), 173 (16), 135 (100). FTIR (ATR): ν = 1636 (CO) cm^-¹. HRMS: m/z calcd [M⁺]: 280.1458; found: 280.1460.
( E )-1-(4-Methoxyphenyl)-2-phenylhex-2-en-1-one (3fb′)
Pale yellow oil. ^¹H NMR (400 MHz, CDCl₃): δ = 0.92 (t, J = 7.2 Hz, 3 H), 1.49 (sext, J = 7.6 Hz, 2 H), 2.24 (q, J = 7.2 Hz, 2 H), 3.85 (s, 3 H), 6.35 (t, J = 7.4 Hz, 1 H), 6.89 (d, J = 9.2 Hz, 2 H), 7.23-7.38 (m, 5 H), 7.81 (d, J = 9.2 Hz, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 13.9, 22.5, 31.4, 55.4, 113.4, 127.3, 128.2, 129.4, 130.8, 132.2, 136.5, 141.6, 142.2, 162.9, 196.1. MS (EI): m/z (%) = 280 (12) [M⁺], 251 (39), 135 (100). FTIR (ATR): ν = 1638 (CO) cm^-¹. HRMS: m/z calcd [M⁺]: 280.1458; found: 280.1460.

8

See Figure [¹] .