Experimental and theoretical investigations on the structure and

Nov 1, 1993 - Darryl D. Dixon and Marcus A. Tius , Lawrence M. Pratt. The Journal of Organic Chemistry 2009 74 (16), 5881-5886. Abstract | Full Text H...
0 downloads 0 Views 1MB Size
6377

J. Org. Chem. 1993,58, 63774389

Experimental and Theoretical Investigations on the Structure and Reactivity of a-Lithiomethoxyallene and Its Grignard Analog Christoph Lambert,+ Paul von Ragu6 Schleyer,'*t and Ernst-Ulrich Wiirthweint Znstitut f u r Organische Chemie der Friedrich- Alexander- Uniuersitst Erlangen-Niirnberg, Henkestrasse 42, 0 - 9 1 0 5 4 Erlangen, Federal Republic of Germany, and Organisch-Chemisches Znstitut der Westfdischen Wilhelms- Universitat Miinster, Orl6ansring 23, 0 - 4 8 1 4 9 Miinster, Federal Republic of Germany Received May 4, 19930

13C NMR, 6Li,1H-HOESY-NMR,and IR spectroscopy of a-lithiomethoxyallene (7) and l-lithio-lethoxy-3-tert-butylallene(8) as well as ab initio model calculations on monomeric and dimeric a-lithiohydroxyallene prove 7 and 8 to be dimeric in THF (7 forms a tetramer in diethyl ether) with a nonclassically l,&bridged structure. Alternative oxygen-coordinated structures could be excluded definitely. Ab initio calculations indicate that the methoxyallene a-Grignard derivative either has a classic allenic structure or an 0-coordinated allenic form (or is a mixture of both) in solution. An alternative propargylic-type isomer is unfavorable energetically. Model computed reactions with hydrogen as the electrophile indicate that the regiospecific a-substitution of a-lithiomethoxyallene is favored kinetically over the y-substitution. In contrast, the reaction of the classic (a-hydroxyalleny1)magnesium hydride with an electrophile leads to the formation of an alkyne (by y-substitution) while that of the 0-coordinated isomer yields the corresponding allene (by a-substitution).

-