(1R,5R)-2,6,6-trimethylbicyclo[3.1.1]hept-2-ene

Conditions: temp:-25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Diisopinocampheylborane was prepared by the method of H. C. Brown et al., Israel J. Chem. 15, 12 (1977) from (+)-α-pinene. To the stirred suspension of diisopinocampheylborane (25 mmol) in tetrahydrofuran at -25° C. was added dropwise 2.4 mL (25 mmol) of 1,3-cyclohexadiene. Monohydroboration of the diene was complete after stirring the reaction mixture at -25° C. for 12 hours, as indicated by the disappearance of the solid diisopinocampheylborane and 11B NMR (δ+80) examination of the solution. The reaction mixture was oxidized with trimethylamine-N-oxide, giving a 92:8 mixture of (-)-2-cyclohexen-1-ol (94% ee) and 3-cyclohexen-1-ol. A second reaction mixture at -78° C. was treated with 25 mm of lithium tert-butyl. Isobutylene was formed and the organoborane was converted into the corresponding borohydride as represented by the following reaction scheme. giving A second reaction mixture at -78° C.

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

Procedure: Followiwng a procedure described in Matsubara, et al., Chem. Abstr., 84:165069b (1976), 64.5 g of dichloroacetic acid was added dropwise over 20 minutes at 5°-6° C. to a magnetically stirred mixture of 68.0 g of (+)-alpha-pinene ([alpha]D +47.1°) and 9.0 g of water. after stirring overnight at 5°-30° C. (ice allowed to melt slowly), the mixture was extracted with 400 ml of methylene chloride. The extract was washed successively with water, aqueous potassium carbonate solution and water, dried and Claisen distilled at 4 mm to give 11.2 g of forecut, b.p. 40°-71° C. and 47.5 g of the desired (+)-alpha-terpineol, b.p. 71°-83° C. Redistillation through a micro Vigreaux column gave 40.5 g of (+)-alpha-terpineol with [alpha]D +79.3° (CHCl3), b.p. 58°-60° C. (1 mm). was extracted with 400 ml of methylene chloride The extract was washed successively with water, aqueous potassium carbonate solution and water dried Claisen distilled at 4 mm

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

Procedure: (E)-(S)-2-Ethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)-2-buten-1-al synthesized from (1R,5R)-α-pinene having an optical purity of 97% e.e. (available from Aldrich) was hydrogenated in the same manner as in Example 2 to obtain the title compound.

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

Procedure: (E)-(S)-2-Methyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)-2-buten-1-al synthesized from (1R,5R)-α-pinene having an optical purity of 97% e.e. (available from Aldrich) was hydrogenated in the same manner as in Example 1 to obtain 3.08 g (yield 80%) of the title compound. The chemical purity of the product was found to be 98% by GC.

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

Procedure: Following a procedure described in Matsubara, et al., Chem. Abstr., 84:165069b (1976), 64.5 g of dichloroacetic acid was added dropwise over 20 minutes at 5°-6° C. to a magnetically stirred mixture of 68.0 g of (+)-alpha-pinene ([alpha]D +47.1°) and 9.0 g of water. After stirring overnight at 5°-30° C. (ice allowed to melt slowly), the mixture was extracted with 400 ml of methylene chloride. The extract was washed successively with water, aqueous potassium carbonate solution and water, dried and Claisen distilled at 4 mm to give 11.2 g of forecut, b.p. 40°-71° C. and 47.5 g of the desired (+)-alpha-terpineol, b.p. 71°-83° C. Redistillation through a micro Vigreaux column gave 40.5 g of (+)-alpha-terpineol with [alpha]D +79.3° (CHCl3), b.p. 58°-60° C. (1 mm). was extracted with 400 ml of methylene chloride The extract was washed successively with water, aqueous potassium carbonate solution and water dried Claisen distilled at 4 mm

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

Procedure: Following a procedure described in Matsubara, et al., Chem. Abstr., 84:165069b (1976), 64.5 g of dichloroacetic acid was added dropwise over 20 minutes at 5°-6° C. to a magnetically stirred mixture of 68.0 g of (+)-alpha-pinene ([alpha]D +47.1°) and 9.0 g of water. After stirring overnight at 5°-30° C. (ice allowed to melt slowly), the mixture was extracted with 400 ml of methylene chloride. The extract was washed successively with water, aqueous potassium carbonate solution and water, dried and Claisen distilled at 4 mm to give 11.2 g of forecut, b.p. 40°-71° C. and 47.5 g of the desired (+)-alpha-terpineol, b.p. 71°-83° C. Redistillation through a micro Vigreaux column gave 40.5 g of (+)-alpha-terpineol with [alpha]D +79.3° (CHCl3), b.p. 58°-60° C. (1 mm). was extracted with 400 ml of methylene chloride The extract was washed successively with water, aqueous potassium carbonate solution and water dried Claisen distilled at 4 mm

Conditions: temp:-25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Diisopinocampheylborane was prepared by the method of H. C. Brown et al., Israel J. Chem. 15, 12 (1977) from (+)-α-pinene. To the stirred suspension of diisopinocampheylborane (25 mmol) in tetrahydrofuran at -25° C. was added dropwise 2.4 mL (25 mmol) of 1,3-cyclohexadiene. Monohydroboration of the diene was complete after stirring the reaction mixture at -25° C. for 12 hours, as indicated by the disappearance of the solid diisopinocampheylborane and 11B NMR (δ+80) examination of the solution. The reaction mixture was oxidized with trimethylamine-N-oxide, giving a 92:8 mixture of (-)-2-cyclohexen-1-ol (94% ee) and 3-cyclohexen-1-ol. A second reaction mixture at -78° C. was treated with 25 mm of lithium tert-butyl. Isobutylene was formed and the organoborane was converted into the corresponding borohydride as represented by the following reaction scheme. giving A second reaction mixture at -78° C.