N-Heterocyclic Carbene Catalyzed Vinylogous Aldol Reaction of 2-(Trimethylsilyloxy)furan and Aldehydes

Abstract

A N-Heterocyclic carbenes (NHC) catalyzed vinylogous aldol reaction between 2-(trimethylsilyloxy)furan and aldehydes has been developed, providing γ-substituted butenolides in high yields with good diastereoselectivities. Furthermore, the catalyst loading can be reduced to 1 mol%.

N-heterocyclic carbenes - vinylogous aldol reaction - butenolides - 2-(trimethylsilyloxy)furan - aldehyde

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20

General Procedure for NHC-Catalyzed Vinylogous Aldol Reaction of 2-(Trimethylsilyloxy)furan with Aldehydes
To a solution of 2 (4.0 mg, 0.012 mmol) in anhyd THF (2.0 mL) was added KOt-Bu (1.1 mg, 0.01 mmol) under N₂. After stirred for 30 min at r.t., the solution was then cooled to 0 ˚C and aldehyde (1.0 mmol) was added followed by 2-(trimethylsilyloxy)furan (1.3 mmol, 200 µL). The reaction mixture was then stirred at r.t. until full consumption of the starting aldehyde as indicated by TLC. The solution was then cooled to 0 ˚C and quenched with 10% aq HCl. The mixture was stirred for 30 min and neutralized by sat. aq NaHCO₃ and then extracted with EtOAc. The combined organic phase was dried over anhyd Na₂SO₄, filtered, and concentrated. The ratio of anti/syn was determined by ^¹H NMR analysis of the crude products, and the configurations were assigned by ^¹H NMR comparison with literature data. The crude products were purified through silica gel chromatography (EtOAc-PE) to afford pure anti products or a mixture of anti/syn isomers.
Data for 8g Yield 83%; white solid; R _f  = 0.14 (PE-EtOAc, 4:1); mp 134.5-135.5 ˚C. ^¹H NMR (400 MHz, CDCl₃): δ = 7.61 (dd, J = 7.6, 1.2 Hz, 1 H), 7.20-7.45 (m, 4 H), 6.20 (dd, J = 5.6, 2.0 Hz, 1 H), 5.62 (t, J = 4.0 Hz, 1 H), 5.36-5.44 (m, 1 H), 3.36 (d, J = 4.4 Hz, 1 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 172.3, 151.2, 134.5, 130.8, 128.6, 126.9, 126.4, 122.5, 83.6, 68.4. IR (KBr): ν = 3390, 1726, 1465, 1437, 1342, 1188, 1108, 1025, 918, 819, 744, 609 cm^-¹. ESI-HRMS: m/z calcd for C₁₁H₉ClO₃Na: 247.0132; found: 247.0156.

21 For recent study of penta- and hexacoordinate silicon-NHC complexes, see: Ghadwal RS. Sen SS. Roesky HW. Tavcar G. Merkel S. Stalke D. Organometallics  2009,  28:  6347