Propylamine → (Z)-1-(tert-butyldimethylsilyl)-6-trimethylsilyl-3-hexen-1,5-diyne

Temperature

23 °C

Tetrakistriphenylphosphine (4.75 g, 4.10 mmol, 0.48 equiv) was added to a solution of (Z)-1-chloro-4-(tert-butyldimethylsilyl)-1-buten-3-yne (17.2 g, 85.7 mmol, 1 equiv) in ether (160 mL) at -78° C. The resulting suspension was deoxygenated by alternately evacuating the reaction vessel and flushing with argon (5×), then was warmed to 23° C. In another flask, copper iodide (2.45 g, 12.8 mmol, 0.15 equiv) was added to a solution of trimethylsilylacetylene (17.0 mL, 120 mmol, 1.40 equiv) and n-propyl amine (27.5 mL, 334 mmol, 3.90 equiv) in ether (100 mL) at -78° C. The solution was deoxygenated (as above, 5×), then was stirred in an ice bath for 10 min causing the light green solution to turn reddish brown. The reddish brown solution was cooled to -78° C. and the palladium-containing suspension prepared above was added over 5 min via a wide-bore cannula. The mixture was deoxygenated (as above, 5×), then was stirred in an ice bath for 3 h and at 23° C. for 1 h. The reaction mixture was partitioned between saturated aqueous ammonium chloride solution (200 mL) and hexanes (300 mL). The aqueous layer was separated and extracted further with hexanes (2×300 mL). The combined organic layers were dried over sodium sulfate and were concentrated. The residue was filtered, then was purified by distillation under reduced pressure (bp 70°-80° C., 0.5 mmHg) to provide (Z)-1-(tert-butyl-dimethylsilyl)-6-trimethylsilyl-3-hexen-1,5-diyne as a light brown oil (20.4 g, 90%). ##STR29##

1. customThe resulting suspension was deoxygenated
2. customby alternately evacuating the reaction vessel
3. customflushing with argon (5×)
4. customThe solution was deoxygenated (as above, 5×),
5. temperatureThe reddish brown solution was cooled to -78° C.
6. additionthe palladium-containing suspension
7. customprepared
8. additionabove was added over 5 min via a wide-bore cannula
9. customThe mixture was deoxygenated (as above, 5×)
10. stirringwas stirred in an ice bath for 3 h and at 23° C. for 1 h
11. customThe reaction mixture was partitioned between saturated aqueous ammonium chloride solution (200 mL) and hexanes (300 mL)
12. customThe aqueous layer was separated
13. extractionextracted further with hexanes (2×300 mL)
14. dry with materialThe combined organic layers were dried over sodium sulfate
15. concentrationwere concentrated
16. filtrationThe residue was filtered
17. distillationwas purified by distillation under reduced pressure (bp 70°-80° C., 0.5 mmHg)

ORD record

ord-ed5dd6e95fc94ab4afbef6f04b5b2a4a

Source dataset

uspto-grants-1998_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05763451