General Experimental for All Chapters

AU microwave experiments were performed using the CEM Discover Synthesizer possessing a single-mode microwave cavity producing controlled irradiation at 2.45 GHz. Experiments were carried out in standard microwave process Pyrex vials (capacity 10 mL) using the high-absorbance level. Reaction time reflects time at the set reaction temperature maintained by cycling of irradiation. 

NMR spectra were recorded a 400, 500 or 600 MHz spectrometer at 101, 126 or 151 MHz. Chemical shifts (5) are reported in parts per million (ppm) downfield 

Phosphonate ester 15 (7.482 g, 19.77 mmol) was placed in a 250 mL round bottom flask and deionised water (55 mL) was added along with potassium carbonate (5.464 g, 39.54 mmol) followed by aqueous formaldehyde (5.93 mL, 79.07 mmol). The reaction mixture was stirred at 80 °C for 48 h. A further addition of aqueous formaldehyde (5.93 mL, 79.07 mmol) and potassium carbonate (5.464 g) was made to drive the reaction to completion, as judged by H-NMR analysis. The reaction was extracted with diethyl ether (2 x 150 mL) and the combined organic layers were washed with H2O (75 mL), brine (75 mL) and dried over anhydrous Na2S04. Excess solvent was removed in vacuo and the cmde product was purified by silica gel column chromatography (pentane/ethyl acetate, 9 1) to yield 14 as a colourless oil (4.550 g, 90 %). 

Ethyl 2-methylenetridecanoate 14 (4.535 g, 17.83 mmol) was dissolved in dry THE (50 mL) under inert atmosphere in a dry 100 mL round bottom flask. The reaction mixture was cooled to -30 °C and DIBAL (26.4 mL, 25 wt% in toluene, 39.23 mmol) was added drop-wise over 40 min and the reaction mixture was stirred for 1 h. The reaction mixture was quenched with diethyl ether (5 mL) and a saturated solution of Rochelle s salt (potassium sodium tartrate) (50 mL). The reaction mixture was stirred for 14 h at room temperature. The product was extracted with diethyl ether (3 x IQO mL). The combined organic layers were washed with H2O (100 mL), brine (100 mL) and dried over anhydrous Na2S04. 

The product was concentrated and purified by silica gel column chromatography (pentane/ethyl acetate, 9 1) to yield alcohol 13 as a colourless oil (3.635 g, 96 %). 

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