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Synlett 2011(17): 2590-2594  
DOI: 10.1055/s-0030-1289519
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Cationic Palladium(II)-Catalyzed Synthesis of 2-Substituted 3-Hydroxymethylbenzo[b]furans

Huan Wang, Xiuling Han*, Xiyan Lu*
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. of China
Fax: +86(21)64166128; e-Mail: xylu@mail.sioc.ac.cn;
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Publication History

Received 29 July 2011
Publication Date:
06 October 2011 (online)

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Abstract

A tandem reaction involving an intramolecular oxypalladation of an alkyne and an addition to the carbonyl group to quench the carbon-palladium bond to complete the catalytic cycle was developed. The reaction was catalyzed with the cationic palladium(II) species without the necessity of a redox system.

Key words

aldehyde - alkyne - cationic palladium(II) complex - 3-hydroxymethylbenzofuran - oxypalladation

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14

General Procedure for the Synthesis of 2-Substituted 3-Hydroxymethylbenzofuran Catalyzed by [Pd(dppp)(H 2 O) 2 ](BF 4 ) 2
A dried small tube with screw-cap was charged with [Pd(dppp)(H2O)2](BF4)2 (1.2 mg, 0.002 mmol), 4 Å MS
(20 mg), THF (0.5 mL), then substrates 1 (0.1 mmol) and aldehydes 2 (0.2 mmol, 2 equiv) were added to the mixture, and the solution was stirred at 45 ˚C until complete consumption of substrates 1 (monitored by TLC). Then,
the mixture was concentrated under reduced pressure and purified by flash column chromatography on silica gel
using EtOAc and PE as the eluent to afford the product.
Compound 3aa: solid; mp 87-89 ˚C. ¹H NMR (400 MHz, CDCl3): δ = 8.16 (d, J = 8.8 Hz, 2 H), 7.77 (d, J = 6.8 Hz, 2 H), 7.65 (d, J = 8.4 Hz, 2 H), 7.52-7.45 (m, 4 H), 7.28-7.23 (m, 1 H), 7.19 (d, J = 7.6 Hz, 1 H), 7.08 (t, J = 7.6 Hz, 1 H), 6.39 (s, 1 H), 2.61 (d, J = 3.6 Hz, 1 H). ¹³C NMR (75 MHz, CDCl3): δ = 154.3, 153.5, 149.1, 147.1, 129.7, 129.5, 129.0, 127.7, 126.9, 124.9, 123.0, 121.0, 116.2, 111.4, 67.7. IR (KBr): ν = 3349, 3065, 1600, 1518, 1453, 1344, 1027, 834, 746 cm-¹. MS (EI): m/z (%) = 345 (100) [M+], 328, 223, 165, 105, 77, 57. HRMS (EI): m/z calcd for C21H15NO4: 345.1001; found: 345.1005.