3,3-Dimethyl-1-butyne → Tert-butylethynyitributylstannane

HRID 484524Notes

Reaction equation

HRID 484524 reaction equation
I/[CH:2]=[CH:3]/CN.[C:6]([C:10]#[CH:11])([CH3:9])([CH3:8])[CH3:7].[CH2:12]([Sn:16](Cl)([CH2:21][CH2:22][CH2:23][CH3:24])[CH2:17][CH2:18][CH2:19][CH3:20])[CH2:13]CC>[H-].[Cl-].[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Zr+2]>[C:6]([CH:10]([Sn:16]([C:12]#[CH:13])([CH2:17][CH2:18][CH2:19][CH3:20])[CH2:21][CH2:22][CH2:23][CH3:24])[CH2:11][CH2:2][CH3:3])([CH3:9])([CH3:8])[CH3:7]

Participants

5

Reactant 3

HCID 135123,3-Dimethyl-1-butyneHCID 15096Tributyltin ChlorideHCID 19917488(E)-3-iodoallyl amine

Product 1

HCID 131718032Tert-butylethynyitributylstannane

Reagents, catalysts & solvents 1

HCID 131718033Bis(cyclopenta-1,3-diene);hydride;zirconium(2+);chlorideCatalyst

Procedure

In Tetrahedron Lett. 29, 1509 (1989), a secondary amine is lithiated at -78° C., then propargyl bromide is reacted thereto to obtain a propargyl amine derivative, which is then subjected to hydrozirconation with zirconocene chloride hydride, and then iodinated to an (E)-3-iodoallyl amine derivative. tert-Butylacetylene is lithiated and then reacted with tributylstannyl chloride at -78° C. to obtain tert-butylethynyltributylstannane, which is then subjected to cross coupling with the above-mentioned (E)-3-iodoallyl amine derivative to obtain an (E)-enyne amine derivative in good yield. However, this method requires n-butyl lithium and a low temperature of -78° C. for the preparation of the propargyl amine derivative, and it also has a drawback that it requires a stoichiometric amount of such a special reagent as zirconocene chloride hydride.

Sources & evidence

ORD record
ord-97f9b78a0ac24677b8d0393b1018015f
Source dataset
uspto-grants-1993_07
Patent number
US05231183

Reaction notes

Loading…