Ti(NMe2)4 as a precatalyst for hydroamination of alkynes with primary amines

Organometallics

Volumn 20, Issue 19, 2001, Pages 3967-3969

  Shi, Yanhui ^a   Ciszewski, James T ^a   Odom, Aaron L ^a  

^a MICHIGAN STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNES; ARYLAMINES; CARBON-CARBON TRIPLE BOND; HYDROAMINATION;

AMINATION; AMINES; CATALYSTS; CHEMICAL BONDS; MOLECULAR STRUCTURE; REACTION KINETICS; SUBSTRATES; SYNTHESIS (CHEMICAL);

ORGANOMETALLICS;

EID: 0035904261     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om010566b     Document Type: Article

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17. 4 is known to produce isolable bridging imido complexes on reaction with primary amines. Thorn, D. L.; Nugent, W. A.; Harlow, R. L. J. Am. Chem. Soc. 1981, 103, 357-363. Excess of amine present under our conditions may support monomeric imido species for reaction with alkynes.
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19. 4 purchased from Strem Chemical, Co. gave comparable results.
20. 4, and 1 equiv of dodecane (internal standard) in toluene was heated to 75°C. The concentration of aniline was 1/3 that used in the reactions of Tables and 1 and 2. All other concentrations are the same. Time to reach the maximum yield of 68% (4:1, Markovnikov:anti-Markovnikov) was <4 h.
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23. 2)(Ph).
24. 2O. Volatiles were removed in vacuo at 60°C. The final product was a red solid soluble in toluene and THF. GPC analysis of the product revealed molecular weights for the polymers produced were as high as 34 000 (n = 333) with smaller chains apparent. A similar reaction with 1-hexyne gave oligomers of undetermined lengths.
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