Silver-Catalyzed Direct Addition of Terminal Alkynes to Simple Cyclic 
Ketones in Water

Zhenhua Jia; Xingshu Li; Albert S. C. Chan; Chao-Jun Li

doi:10.1055/s-0032-1317342

Synlett, Table of Contents

Synlett 2012; 23(19): 2758-2762
DOI: 10.1055/s-0032-1317342

cluster

Silver-Catalyzed Direct Addition of Terminal Alkynes to Simple Cyclic Ketones in Water

Authors

Zhenhua Jia

^aDepartment of Chemistry and FQRNT Center for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street West, Montreal, QC, H3A 0B8, Canada Fax: +1(514)3983797 Email: cj.li@mcgill.ca

^bInstitute of Drug Synthesis and Pharmaceutical Process, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, P. R. of China
Xingshu Li

^bInstitute of Drug Synthesis and Pharmaceutical Process, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, P. R. of China
Albert S. C. Chan

^bInstitute of Drug Synthesis and Pharmaceutical Process, School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006, P. R. of China
Chao-Jun Li*

^aDepartment of Chemistry and FQRNT Center for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street West, Montreal, QC, H3A 0B8, Canada Fax: +1(514)3983797 Email: cj.li@mcgill.ca

Abstract

All articles of this category

Abstract

The first catalytic addition of terminal alkynes to simple cyclic ketones in water catalyzed by silver was developed. Cyclic ketones were reacted with terminal alkynes efficiently in water to give the corresponding propargyl alcohols.

Key words

Grignard-type reactions in water - silver catalysis - ketone–alkyne addition - propargyl alcohol

Full Text

References

References
1 For a monograph, see: Blomberg C. The Barbier Reaction and Related One-Step Processes . In Reactivity and Structure: Concepts in Organic Chemistry . Hafner K, Lehn JM, Rees CW, von Ragué Schleyer P, Trost BM, Zahradnîk R. Springer Verlag; Berlin: 1993

For reviews, see:

2a Chan T.-H, Li L, Yang Y, Lu W. Clean Solvents, Alternative Media for Chemical Reactions and Processing, ACS Symposium Series 819. Abraham MA, Moens L. Washington: 2002: 166
2b Li C.-J, Chan T.-H. Comprehensive Organic Reactions in Aqueous Media. Wiley; New York: 2007

For selected examples from our lab, see:

2c Li C.-J. Tetrahedron 1996; 52: 5643
2d Li C.-J. Chem. Rev. 2005; 105: 3095
2e Meng Y, Li C.-J. J. Am. Chem. Soc. 2000; 120: 9538
2f Chan T.-H, Yang Y, Li C.-J. J. Org. Chem. 1999; 64: 4452
2g Venkatraman S, Li C.-J. Tetrahedron Lett. 2001; 42: 781
2h Li C.-J, Chen DL, Lu YQ, Haberman JX, Mague JT. J. Am. Chem. Soc. 1996; 118: 4216
2i Chan T.-H, Li C.-J, Wei ZY. J. Chem. Soc., Chem. Commun. 1990; 505
2j Li C.-J, Zhang WC. J. Am. Chem. Soc. 1998; 120: 9102
2k Keh CC. K, Wei C, Li C.-J. J. Am. Chem. Soc. 2003; 125: 4062

3a Trost BM. Science 1991; 254: 1471
3b Trost BM. Angew. Chem. Int. Ed. 1995; 34: 259

For examples, see:

4a Carreira EM, Frantz DE, Fässler R, Tomooka CS. Acc. Chem. Res. 2000; 33: 373
4b Trost BM, Sorum MT, Chan C, Harms AE, Ruhter G. J. Am. Chem. Soc. 1997; 119: 698
4c Yamaguchi M, Hayashi A, Minami T. J. Org. Chem. 1991; 56: 4091
4d Han Y, Huang Y.-Z. Tetrahedron Lett. 1995; 36: 7277
4e Trost BM, Weiss AH. Adv. Synth. Catal. 2009; 351: 963

5a Wei C, Li C.-J. Green Chem. 2002; 4: 39
5b Chen L, Li C.-J. Adv. Synth. Catal. 2006; 348: 1459

6 Li C.-J. Acc. Chem. Res. 2010; 43: 581

7a Li C.-J, Wei C. Chem. Commun. 2002; 268

For asymmetric addition, see:

7b Wei C, Li C.-J. J. Am. Chem. Soc. 2002; 124: 5638
7c Wei C, Mague JT, Li C.-J. Proc. Natl. Acad. Sci. U.S.A. 2004; 101: 5749

8a Wei C, Li C.-J. J. Am. Chem. Soc. 2003; 125: 9584
8b Huang B, Yao X, Li C.-J. Adv. Synth. Catal. 2006; 348: 1528
8c Wei CM, Li ZG, Li C.-J. Org. Lett. 2003; 5: 4473
8d For a recent review, see: Yoo W.-J, Zhao L, Li C.-J. Aldrichimica Acta 2011; 44: 43
8e Wei C, Li Z, Li C.-J. Synlett 2004; 1472
8f Zani L, Bolm C. Chem. Commun. 2006; 4263
8g Peshkov VA, Pereshivko OP, Van der Eycken EV. Chem. Soc. Rev. 2012; 41: 3702

9 Zhang J, Wei C, Li C.-J. Tetrahedron Lett. 2002; 43: 5731
10 Chen L, Li C.-J. Org. Lett. 2004; 6: 3151

11a Chen L, Li C.-J. Tetrahedron Lett. 2004; 45: 2771
11b Chen L, Li C.-J. Chem. Commun. 2004; 2362

See also:

11c Carreira EM, Knopfel TF. J. Am. Chem. Soc. 2003; 125: 6054
11d Knopfel TF, Zarotti P, Ichikawa T, Carreira EM. J. Am. Chem. Soc. 2005; 127: 9682
11e Zhou L, Chen L, Skouta R, Li C.-J. Org. Biomol. Chem. 2008; 6: 2969

12 For a review, see: Li Z, Carpretto DA, He C. In Progress in Inorganic Chemistry . Vol. 56. Karlin KD. John Wiley & Sons; New York: 2009

13a Yao X, Li C.-J. Org. Lett. 2005; 7: 4395
13b Deng G, Li C.-J. Synlett 2008; 1571
13c Yu M, Skouta R, Zhou L, Jiang H.-F, Yao X, Li C.-J. J. Org. Chem. 2009; 74: 3378

14 Fu X.-P, Liu L, Wang D, Chen Y.-J, Li C.-J. Green Chem. 2011; 13: 549
15 Yao X, Li C.-J. Org. Lett. 2006; 8: 1953

16a Billingsley K, Buchwald SL. J. Am. Chem. Soc. 2007; 129: 3358

For reviews, see:

16b Mauger CC, Mignani GA. Aldrichimica Acta 2006; 39: 17
16c Schlummer B, Scholz U. Adv. Synth. Catal. 2004; 346: 1599

17 General Reaction Procedure: Degassed CH₂Cl₂ (0.25 mL) was added to a microwave tube containing the ligand RuPhos (23.2 mg, 0.05 mmol) and AgCl (3.6 mg, 0.025 mmol) under argon. The resulting suspension was stirred at r.t. until a clear, colorless solution was obtained; then the solvent was removed under vacuum. Cyclohexanone (1a; 26 μL, 0.25 mmol), DBU (7.5 μL, 0.05 mmol) and degassed H₂O (0.5 mL) were subsequently added under argon followed by the addition of phenylacetylene (2a; 104 μL, 1 mmol) using a syringe pump over 12 h. The reaction mixture was stirred for another 12 h at 100 °C, then cooled and extracted with EtOAc (3 × 10 ml). The combined organic phase was concentrated and purified by flash column chromatography on silica gel (hexane–EtOAc, 10:1) to give the desired product 3a as a white solid (40 mg, 80%). The NMR data are in full agreement with those previously reported in the literature.¹⁸1H NMR (400 MHz, CDCl3): δ = 7.41–7.43 (m, 2 H), 7.26–7.30 (m, 3 H), 1.99–2.03 (m, 3 H), 1.57–1.77 (m, 7 H), 1.28 (m, 1 H). 13C NMR (CDCl3, 75 MHz) δ = 131.7, 128.3, 128.1, 122.9, 93.8, 83.6, 72.2, 43.2, 28.0, 22.3.��
18 Yasukawa T, Miyamura H, Kobayashi S. Org. Biomol. Chem. 2011; 9: 6208