Synlett 2012; 23(9): 1331-1334
DOI: 10.1055/s-0031-1290690
letter
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Carbamoylacetates from α-Iodoacetate, CO, and Amines under Pd/Light Combined Conditions

Shuhei Sumino
Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Email: ryu@c.s.osakafu-u.ac.jp
,
Akira Fusano
Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Email: ryu@c.s.osakafu-u.ac.jp
,
Takahide Fukuyama
Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Email: ryu@c.s.osakafu-u.ac.jp
,
Ilhyong Ryu*
Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Sakai, Osaka 599-8531, Japan, Email: ryu@c.s.osakafu-u.ac.jp
› Author Affiliations
Further Information

Publication History

Received: 19 February 2012

Accepted after revision: 14 March 2012

Publication Date:
14 May 2012 (online)


Abstract

We developed a novel synthetic method of carbamoylacetates from α-iodoacetate, carbon monoxide, and amines under photoirradiation conditions in the presence of a Pd catalyst. This reaction likely proceeds via interplay of radical and organopalladium species.

 
  • References

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  • 10 General Procedure for the Synthesis of 3a A magnetic stirring bar, 1 (54.1 mg, 0.25 mmol), 2a (92.9 mg, 0.77 mmol), Et3N (29.9 mg, 0.30 mmol), PdCl2(PPh3)2 (8.4 mg, 0.012 mmol), DMAP (3.7 mg, 0.031 mmol), toluene (5.0 mL), and H2O (50 μL) were placed in a stainless steel autoclave for photoreaction equipped with an inserted Pyrex glass liner. The autoclave was closed, purged three times with 10 atm of CO, pressurized with 10 atm of CO, and then irradiated by two 15 W black lights with stirring for 8 h. Excess CO was discharged after the reaction. The reaction mixture was added to H2O (20 mL) and extracted with Et2O (3 × 20 mL). The combined ether layer was washed with brine, and dried over MgSO4, then filtered and concentrated in vacuo. The resulting residue was subjected to silica gel column chromatography using hexane–Et2O as eluent affording 3a (45.8 mg, 77%).1H NMR (400 MHz, CDCl3): δ = 7.45–7.35 (m, 3 H), 7.20 (d, J = 6.8 Hz, 2 H), 4.05 (q, J = 7.2 Hz, 2 H), 3.78 (q, J = 7.2 Hz, 2 H), 1.23 (t, J = 7.2 Hz, 3 H), 1.14 (t, J = 7.2 Hz, 3 H). 13C NMR (100 MHz, CDCl3): δ = 12.89, 14.06, 41.96, 44.25, 61.20, 128.38, 129.81, 141.77, 165.47, 167.83. IR (neat): 1740, 1667, 1404, 1368 cm–1. MS: m/z (%) = 235 (55) [M+], 190 (16), 148 (21), 121 (49), 120 (44), 105 (100), 104 (12), 77 (23). HRMS (EI): m/z calcd for C13H17NO3 [M]+: m/z = 235.1208; found: 235.1213