Monoterpenoid Synthesis by Transition Metal Catalyzed Coupling of Enediylmagnesium with C5-Organic Halides

Kajihara, Yasushi; Ishikawa, Katsuhiro; Yasuda, Hajime; Nakamura, Akira

doi:10.1246/bcsj.53.3035

Cited by 11 publications

(6 citation statements)

References 4 publications

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“…Found: C, 76.43; , 7.90; N, 15.67. l,8-Bis(dimethylamino)-l,8-dicyano-l,8-diphenyloctane (4a). By use of the same procedure, the reaction of a-(dimethylamino)-a-phenylacetonitrile (la; 1.282 g, 8 mmol) with 1,6-dibromohexane (0.976 g, 4 mmol) was carried out to give 1.419 g (88% yield) of 4a: mp 98-100 °C; IR (KBr) xCN 2230 cm"1; NMR (CDClg) 8 1.05 (br s, 8 ), 1.50-2.0 (br m, 4 H), 2.25 (s, 12 H), 7.40 (s-like, 10 H). Anal.…”

Section: Methodsmentioning

confidence: 99%

“…2.5-Bis(dimethylamino)-2,5-bis(4-methoxyphenyl)adiponitrile (13a). By use of the same procedure, the reaction of a-(dimethylamino)-a-(4-methoxyphenyl)acetonitrile (10a; 1.522 g, 8 mmol) with 1,2-dibromoethane (0.752 g, 4 mmol) was carried out to give 0.602 g (37% yield) of 13a: mp 137-139 °C; IR (KBr) .-on 2240 cm"1; NMR (CDClg) 8 1.78 (s, 4 ), 2.16 (s, 12 H), 3.85 (s, 6 ), 6.90 (d, 4 H, J =9 Hz), 7.38 (d, 4 H, J = 9 Hz).…”

Section: Methodsmentioning

confidence: 99%

“…NMR (CDClg) 8 1.95 (s, 4 ), 2.30 (s, 12 ), 7.01 (t, 2 H, J = 4 Hz), 7.25-7.55 (m, 4 H). Anal Caled for C18HaaN4S2: C, 60.30; , 6.18; N, 15.63.…”

Section: Methodsmentioning

confidence: 99%

“…NMR (CDClg) 8 1.58 (t-like, 4 H, J = 6 Hz), 1.80-2.20 (m, 2 H), 2.28 (s, 12 H), 6. 90 (t, 2 H, J = 5 Hz), 7.18 (d, 2 H, «7= 5 Hz), 7.32 (d, 2 H, J = 5 Hz).…”

Section: Methodsmentioning

confidence: 99%

“…2.3-Dimorpholino-2,3-diphenylsuccinonitrile (21) and 2-Morpholino-2-phenyl-3-butenenitrile (23). By use of the same procedure, the reaction of a-morpholino-a-phenylacetonitrile (Id; 1.618 Physical properties of 23 are as follows: viscous oil; IR (KBr) í-cn 2260 cm"1; NMR (CDClg) 8 2.55 (t, 2 H, J = 4 Hz), 2.64 (t, 4 H, J = 4 Hz), 3.75 (t, 4 H, J = 4 Hz), 5.30 (dd, 1 H, J = 8,3 Hz), 5.80 (d, 1 H, J = 3 Hz), 5.85 (d, 1 H, J = 8 Hz), 7.3-7.S (m, 5 H); MS, m/e 228 (M+•). Anal.…”

Section: Methodsmentioning

confidence: 99%

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An efficient method for synthesis of symmetrical diketones via reaction of .alpha.-amino-.alpha.-arylacetonitriles (masked acyl anion equivalents) with alkyl dibromides

Takahashi¹,

Matsuzaki²,

Ogura³

et al. 1983

J. Org. Chem.

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Reduction of 1 to 3. A solution of 14.3 mg of 1 in 1 mL of absolute ethanol was treated with 5 mg of NaBH4. The mixture was stirred at room temperature for 80 min and then quenched with several drops of 5% HC1. After addition of 3 mL of water, the product was extracted four times with 3-mL portions of diethyl ether and then dried over anhydrous K2C03. Filtration and evaporation of solvent left 12.7 mg of nearly pure 3, which after HPLC had [o]D 24.3°( c 1.07, CHC13).Reduction of 2 to 4. This was analogous to preparation of 3 from 1 above. From 25 mg 2, 22 mg of crude 4 was obtained. After purification by HPLC, its spectral properties matched those of natural 4.Acetylation of 3 to 4. To a solution of 13.0 mg of 3 in 1 mL of dry pyridine, 50 µ * of freshly distilled acetic anhydride was added, and the reaction was allowed to proceed at room temperature for 17 h. Methylene chloride (10 mL) was added, and the solution was washed with 10% HC1 (2X), saturated CuS04 (2x), and H20 (IX) to remove the pyridine. After drying with anhydrous MgS04 and removal of solvent, 12 mg of 4 remained, about 95% pure by *H NMR. This material was purified by HPLC on Partisil M9 and Lichrosorb-ODS. From natural 3, [a]D 14.2°(c 1.21, CHC13); from synthetic 3, [a]D 20.5°(c 0.57, CHC13).

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

“…NMR (CDClg) 8 1.95 (s, 4 ), 2.30 (s, 12 ), 7.01 (t, 2 H, J = 4 Hz), 7.25-7.55 (m, 4 H). Anal Caled for C18HaaN4S2: C, 60.30; , 6.18; N, 15.63.…”

Section: Methodsmentioning

confidence: 99%

“…NMR (CDClg) 8 1.58 (t-like, 4 H, J = 6 Hz), 1.80-2.20 (m, 2 H), 2.28 (s, 12 H), 6. 90 (t, 2 H, J = 5 Hz), 7.18 (d, 2 H, «7= 5 Hz), 7.32 (d, 2 H, J = 5 Hz).…”

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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