benzyl 5-bromopentanoate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of benzyl 5-bromovalerate (2.27 g, 8.4 mmol) and the silver salt of 2-hydroxy-1,4-naphthoquinone (1.63 g, 5.81 mmol) in benzene (8 mL) was stirred for 48 h at 55° C. and filtered through celite. The filtrate was diluted with diethyl ether, extracted with a 20% aqueous solution of NaHSO3 then basified to pH 10-11 with Na2CO3, and extracted with CH2Cl2. Yellow solid (1.334 g, 63%). 1H NMR (CDCl3) 8.12 (d, J=7.5 Hz, 1H), 7.85 (d, J=7.7 Hz, 1H), 7.68 (t, J=7.5, 1H), 7.58 (t, J=7.7 Hz, 1H), 7.25-7.50 (m, 5H), 5.93 (s, 1H), 5.14 (s, 2H), 4.15 (t, J=5.7 Hz, 2H), 2.50 (t, J=7.0 Hz, 2H), 1.8-2.2 (m, 4H). filtered through celite The filtrate was diluted with diethyl ether extracted with a 20% aqueous solution of NaHSO3 extracted with CH2Cl2

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of benzyl 5-bromovalerate (2.27 g, 8.4 mmol) and the silver salt of 2-hydroxy-1,4-naphthoquinone (1.63 g, 5.81 mmol) in benzene (8 mL) was stirred for 48 h at 55° C. and filtered through celite. The filtrate was diluted with diethyl ether, extracted with a 20% aqueous solution of NaHSO3 then basified to pH 10-11 with Na2CO3, and extracted with CH2Cl2. Yellow solid (1.334 g, 63%). 1H NMR (CDCl3) 8.12 (d, J=7.5 Hz, 1H), 7.85 (d, J=7.7 Hz, 1H), 7.68 (t, J=7.5, 1H), 7.58 (t, J=7.7 Hz, 1H), 7.25-7.50 (m, 5H), 5.93 (s, 1H), 5.14 (s, 2H), 4.15 (t, J=5.7 Hz, 2H), 2.50 (t, J=7.0 Hz, 2H), 1.8-2.2 (m, 4H). filtered through celite The filtrate was diluted with diethyl ether extracted with a 20% aqueous solution of NaHSO3 extracted with CH2Cl2

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of benzyl 5-bromovalerate (2.27 g, 8.4 mmol) and the silver salt of 2-hydroxy-1,4-naphthoquinone (1.63 g, 5.81 mmol) in benzene (8 mL) was stirred for 48 h at 55° C. and filtered through celite. The filtrate was diluted with diethyl ether, extracted with a 20% aqueous solution of NaHSO3 then basified to pH 10-11 with Na2CO3, and extracted with CH2Cl2. Yellow solid (1.334 g, 63%). 1H NMR (CDCl3) 8.12 (d, J=7.5 Hz, 1H), 7.85 (d, J=7.7 Hz, 1H), 7.68 (t, J=7.5, 1H), 7.58 (t, J=7.7 Hz, 1H), 7.25-7.50 (m, 5H), 5.93 (s, 1H), 5.14 (s, 2H), 4.15 (t, J=5.7 Hz, 2H), 2.50 (t, J=7.0 Hz, 2H), 1.8-2.2 (m, 4H). filtered through celite The filtrate was diluted with diethyl ether extracted with a 20% aqueous solution of NaHSO3 extracted with CH2Cl2

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of benzyl 5-bromovalerate (2.27 g, 8.4 mmol) and the silver salt of 2-hydroxy-1,4-naphthoquinone (1.63 g, 5.81 mmol) in benzene (8 mL) was stirred for 48 h at 55° C. and filtered through celite. The filtrate was diluted with diethyl ether, extracted with a 20% aqueous solution of NaHSO3 then basified to pH 10-11 with Na2CO3, and extracted with CH2Cl2. Yellow solid (1.334 g, 63%). 1H NMR (CDCl3) 8.12 (d, J=7.5 Hz, 1H), 7.85 (d, J=7.7 Hz, 1H), 7.68 (t, J=7.5, 1H), 7.58 (t, J=7.7 Hz, 1H), 7.25-7.50 (m, 5H), 5.93 (s, 1H), 5.14 (s, 2H), 4.15 (t, J=5.7 Hz, 2H), 2.50 (t, J=7.0 Hz, 2H), 1.8-2.2 (m, 4H). filtered through celite The filtrate was diluted with diethyl ether extracted with a 20% aqueous solution of NaHSO3 extracted with CH2Cl2

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of benzyl 5-bromovalerate (2.27 g, 8.4 mmol) and the silver salt of 2-hydroxy-1,4-naphthoquinone (1.63 g, 5.81 mmol) in benzene (8 mL) was stirred for 48 h at 55° C. and filtered through celite. The filtrate was diluted with diethyl ether, extracted with a 20% aqueous solution of NaHSO3 then basified to pH 10-11 with Na2CO3, and extracted with CH2Cl2. Yellow solid (1.334 g, 63%). 1H NMR (CDCl3) 8.12 (d, J=7.5 Hz, 1H), 7.85 (d, J=7.7 Hz, 1H), 7.68 (t, J=7.5, 1H), 7.58 (t, J=7.7 Hz, 1H), 7.25-7.50 (m, 5H), 5.93 (s, 1H), 5.14 (s, 2H), 4.15 (t, J=5.7 Hz, 2H), 2.50 (t, J=7.0 Hz, 2H), 1.8-2.2 (m, 4H). filtered through celite The filtrate was diluted with diethyl ether extracted with a 20% aqueous solution of NaHSO3 extracted with CH2Cl2

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of benzyl 5-bromovalerate (2.27 g, 8.4 mmol) and the silver salt of 2-hydroxy-1,4-naphthoquinone (1.63 g, 5.81 mmol) in benzene (8 mL) was stirred for 48 h at 55° C. and filtered through celite. The filtrate was diluted with diethyl ether, extracted with a 20% aqueous solution of NaHSO3 then basified to pH 10-11 with Na2CO3, and extracted with CH2Cl2. Yellow solid (1.334 g, 63%). 1H NMR (CDCl3) 8.12 (d, J=7.5 Hz, 1H), 7.85 (d, J=7.7 Hz, 1H), 7.68 (t, J=7.5, 1H), 7.58 (t, J=7.7 Hz, 1H), 7.25-7.50 (m, 5H), 5.93 (s, 1H), 5.14 (s, 2H), 4.15 (t, J=5.7 Hz, 2H), 2.50 (t, J=7.0 Hz, 2H), 1.8-2.2 (m, 4H). filtered through celite The filtrate was diluted with diethyl ether extracted with a 20% aqueous solution of NaHSO3 extracted with CH2Cl2

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of benzyl 5-bromovalerate (2.27 g, 8.4 mmol) and the silver salt of 2-hydroxy-1,4-naphthoquinone (1.63 g, 5.81 mmol) in benzene (8 mL) was stirred for 48 h at 55° C. and filtered through celite. The filtrate was diluted with diethyl ether, extracted with a 20% aqueous solution of NaHSO3 then basified to pH 10-11 with Na2CO3, and extracted with CH2Cl2. Yellow solid (1.334 g, 63%). 1H NMR (CDCl3) 8.12 (d, J=7.5 Hz, 1H), 7.85 (d, J=7.7 Hz, 1H), 7.68 (t, J=7.5, 1H), 7.58 (t, J=7.7 Hz, 1H), 7.25-7.50 (m, 5H), 5.93 (s, 1H), 5.14 (s, 2H), 4.15 (t, J=5.7 Hz, 2H), 2.50 (t, J=7.0 Hz, 2H), 1.8-2.2 (m, 4H). filtered through celite The filtrate was diluted with diethyl ether extracted with a 20% aqueous solution of NaHSO3 extracted with CH2Cl2

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of benzyl 5-bromovalerate (2.27 g, 8.4 mmol) and the silver salt of 2-hydroxy-1,4-naphthoquinone (1.63 g, 5.81 mmol) in benzene (8 mL) was stirred for 48 h at 55° C. and filtered through celite. The filtrate was diluted with diethyl ether, extracted with a 20% aqueous solution of NaHSO3 then basified to pH 10-11 with Na2CO3, and extracted with CH2Cl2. Yellow solid (1.334 g, 63%). 1H NMR (CDCl3) 8.12 (d, J=7.5 Hz, 1H), 7.85 (d, J=7.7 Hz, 1H), 7.68 (t, J=7.5, 1H), 7.58 (t, J=7.7 Hz, 1H), 7.25-7.50 (m, 5H), 5.93 (s, 1H), 5.14 (s, 2H), 4.15 (t, J=5.7 Hz, 2H), 2.50 (t, J=7.0 Hz, 2H), 1.8-2.2 (m, 4H). filtered through celite The filtrate was diluted with diethyl ether extracted with a 20% aqueous solution of NaHSO3 extracted with CH2Cl2

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a dry, nitrogen purged 100 mL round bottomed flask was added benzyl alcohol (2.98 g, 0.027 mol), triethylamine (2.79 g, 0.027 mol) and CH2Cl2 (50 mL). The solution was stirred and cooled to 0° C. and 5-bromovaleryl chloride (5.00 g, 0.025 mol) added dropwise. A white suspension formed and this mixture was stirred at 0° C. for 0.5 h then warmed to rt over 1 h. After stirring at rt for 15 h, the suspension was poured into water (100 mL) and the phases separated. The aqueous layer was extracted with CH2Cl2 (1×100 mL) and the combined CH2Cl2 layers were dried over Na2SO4. Filtration and concentration produced a light brown suspension, which was diluted with EtOAc (50 mL) and then re-filtered. After concentration, the resulting amber oil was chromatographed on silica gel using 10% EtOAc in hexanes to give 6.79 g (100%) of Preparation 12 as a clear, colorless oil. Rf=0.80 (SiO2, 50% EtOAc in hexanes). 1H NMR (500 MHz, CDCl3): δ=7.33 (m, 5H), 5.11 (s, 2H), 3.38 (t, J=6.5 Hz, 2H), 2.38 (t, J=7.0 Hz, 2H), 1.88 (m, 2H) and 1.79 (m, 2H). To a dry, nitrogen purged 100 mL round bottomed flask A white suspension formed this mixture was stirred at 0° C. for 0.5 h then warmed to rt over 1 h After stirring at rt for 15 h the phases separated The aqueous layer was extracted with CH2Cl2 (1×100 mL) the combined CH2Cl2 layers were dried over Na2SO4 Filtration and concentration produced a light brown suspension, which re-filtered After concentration the resulting amber oil was chromatographed on silica gel using 10% EtOAc in hexanes to give 6.79 g (100%) of Preparation 12 as a clear, colorless oil

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This compound was prepared from the products of 8a (0.73 g; 2.7 mmol) and 8b (1.0 g; 2.5 mmol) according to Procedure C. The crude product was purified on a 75×45 mm silica gel 60 column eluted with ethyl acetate-hexane (1:1) (1000 mL) collecting 13×50 mL fractions. Fractions containing the product (5-8) were collected, and after evaporation 0.82 g (72%) product was obtained (yellowish solid, mp 53-56° C.). The crude product was purified on a 75×45 mm silica gel 60 column eluted with ethyl acetate-hexane (1:1) (1000 mL) collecting 13×50 mL fractions Fractions containing the product (5-8) were collected after evaporation 0.82 g (72%) product was obtained (yellowish solid, mp 53-56° C.)