Cyclization-Carbonylation-Cyclization Coupling Reaction of Propargyl Ureas with Palladium(II)-Bisoxazoline Catalyst
Abstract
:1. Introduction
2. Results and Discussion
2.1. Optimization Studies
Entry | Catalyst(5 mol %) | Conditions | Yield of4a (%) | Yield of2a (%) |
---|---|---|---|---|
1 | (CH3CN)2PdCl2 | rt, 24 h | 4a: 46 | 2a: 36 |
2 | Pd(tfa)2 | −20 °C, 24 h | 4a: 24 | 2a: 20 |
3 | [Pd(bipy)Cl2] | rt, 24 h | 4a: 29 | 2a: 13 |
4 | (Ph3P)2PdCl2 | rt, 19 h | 4a: 16 | 2a: 61 |
5 | Pd(PPh3)4 | rt, 24 h | - | 2a: 44 |
6 | [Pd(L)(tfa)2] | rt, 24 h | 4a: 83 | 2a: 17 |
7 | [Pd(L)(tfa)2] | 50 °C, 3 h | 4a: 61 | 2a: 21 |
8 | [Pd(L)(tfa)2] | −20 °C, 24 h | 4a: 30 | 2a: 29 |
9 a | [Pd(L)(tfa)2] | rt, 24 h | N.R. | |
10 b | [Pd(L)(tfa)2] | rt, 24 h | N.R. |
2.2. Substrate Scope and Limitations
Entry | R1 | R2 | Conditions | Yield of4 (%) | Yield of2 (%) |
---|---|---|---|---|---|
1 | Me | nPr | rt, 24 h | 4a: 83 | 2a: 17 |
2 | Me | Bn | rt, 18 h | 4b: 73 | 2b: 10 |
3 | Me | nBu | rt, 20 h | 4c: 61 | 2c: 25 |
4 | Me | Phenethyl | 7 °C, 48 h | 4d: 58 | 2d: 20 |
5 | Me | Cyclohexyl | rt, 24 h | 4e: 66 | 2e: 30 |
6 | -(CH2)5- | Phenethyl | rt, 24 h | 4f: 89 | 2f: 11 |
7 | -(CH2)5- | Cyclohexyl | rt, 24 h | 4g: 74 | 2g: 20 |
8 | -(CH2)5- | Ph | rt, 40 h | 4h: 24 | 2h: 23 |
9 a | -(CH2)5- | H | rt, 48 h | N.R. | |
10 | H | Phenethyl | rt, 24 h | N.R. |
2.3. Preparation of [Pd(L)(tfa)2]
3. Experimental
3.1. General
3.2. Preparation of Substrates 1a–j
3.3. General Procedure for the CCC-Coupling Reaction of 1
3.3.1. Dimeric Ketone 4a
3.3.2. (2E)-Methyl 2-[4,4-dimethyl-2-(propylamino)-5(4H)-oxazolylidene]acetate (2a)
3.3.3. Dimeric Ketone 4b
3.3.4. (2E)-Methyl 2-[4,4-dimethyl-2-(phenylmethylamino)-5(4H)-oxazolylidene]acetate (2b)
3.3.5. Dimeric Ketone 4c
3.3.6. (2E)-Methyl 2-[4,4-dimethyl-2-(butylamino)-5(4H)-oxazolylidene]acetate (2c)
3.3.7. Dimeric Ketone 4d
3.3.8. (2E)-Methyl 2-[4,4-dimethyl-2-(phenylethylamino)-5(4H)-oxazolylidene]acetate (2d)
3.3.9. Dimeric Ketone 4e
3.3.10. (2E)-Methyl 2-[4,4-dimethyl-2-(cyclohexylethylamino)-5(4H)-oxazolylidene]acetate (2e)
3.3.11. Dimeric Ketone 4f
3.3.12. Monomeric Ester 2f
3.3.13. Dimeric Ketone 4g
3.3.14. Monomeric Estere 2g
3.3.15. Dimeric Ketone 4h
3.3.16. Dimeric Ketone 2h
3.4. Preparation of Ligands and Racemic-[Pd(L)(tfa)2]
3.4.1. Preparation of L and L′
3.4.2. Preparation of [Pd(L)(tfa)2]
4. Conclusions
Supplementary Materials
Acknowledgments
References
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Kusakabe, T.; Kawaguchi, K.; Kawamura, M.; Niimura, N.; Shen, R.; Takayama, H.; Kato, K. Cyclization-Carbonylation-Cyclization Coupling Reaction of Propargyl Ureas with Palladium(II)-Bisoxazoline Catalyst. Molecules 2012, 17, 9220-9230. https://doi.org/10.3390/molecules17089220
Kusakabe T, Kawaguchi K, Kawamura M, Niimura N, Shen R, Takayama H, Kato K. Cyclization-Carbonylation-Cyclization Coupling Reaction of Propargyl Ureas with Palladium(II)-Bisoxazoline Catalyst. Molecules. 2012; 17(8):9220-9230. https://doi.org/10.3390/molecules17089220
Chicago/Turabian StyleKusakabe, Taichi, Koujiro Kawaguchi, Miya Kawamura, Naohiko Niimura, Rong Shen, Hiroyuki Takayama, and Keisuke Kato. 2012. "Cyclization-Carbonylation-Cyclization Coupling Reaction of Propargyl Ureas with Palladium(II)-Bisoxazoline Catalyst" Molecules 17, no. 8: 9220-9230. https://doi.org/10.3390/molecules17089220