t-Butoxybis(dimethylamino)methane

Abstract

1 tert-Butoxybis(dimethylamino)methane 1 CH RO NMe 2 NMe 2 (1; R = t-Bu) (t-BAE) [5815-08-7] C 9 H 22 N 2 O (MW 174.33) InChI = 1/C9H22N2O/c1-9(2,3)12-8(10(4)5)11(6)7/h8H,1-7H3 InChIKey = HXRAMSFGUAOAJR-UHFFFAOYAR (2; R = Me) (MAE) [1186-70-5] C 6 H 16 N 2 O (MW 132.24) InChI = 1/C6H16N2O/c1-7(2)6(9-5)8(3)4/h6H,1-5H3 InChIKey = NCIMAYPZWJQYGN-UHFFFAOYAO (aminal esters reactive as aminomethylenating reagents (formylating reagents) for CH 2 -and NH 2 -acidic compounds. The t-butyl analog is somewhat more reactive than the methyl derivative; bis(dimethylamino)carbene can be generated from both compounds) Alternate Name: Bredereck's reagent. Physical Data: (1) bp 50-52 • C/12 mmHg; n 20 D = 1.4250. (2) bp 128 • C/760 mmHg; 32-33 • C/25 mmHg; n 20 D = 1.4158. Solubility: miscible with nonpolar aprotic waterfree solvents (benzene, toluene, cyclohexane, diethyl ether, etc.); react with protic solvents like water (hydrolysis to DMF) or alcohols (alcoholysis affords DMF acetals). Even common solvents like acetonitrile or acetone which are weakly CH-acidic react with the aminal esters on heating. Form Supplied in: colorless to weak yellow, strong aminesmelling liquids. Analysis of Reagent Purity: the best method is 1 H NMR spectroscopic examination of a neat sample. Handling, Storage, and Precautions: both compounds should be handled in a fume hood, with strict exclusion of atmospheric moisture. They should be stored in tightly sealed containers in a refrigerator under an atmosphere of dry nitrogen or argon.Introduction. Alkoxybis(dimethylamino)methanes can be obtained in good yields from N,N,N ,N -tetraalkylformamidinium salts and alcohol-free alkoxides. 2 The reactions have to be conducted in inert, strictly anhydrous solvents like cyclohexane, hexane, ether, or THF, in which unfortunately both reagents are insoluble. As a consequence it is necessary to use relatively large amounts of the solvent and long reaction times (eq 1). In the patent literature it is claimed that by the use of a mixture of DMF and mesitylene as solvent, the yields can be improved to about 95%. 3 In another method, 4 bis(dimethylamino)acetonitrile is used as the starting compound. Alcohol-free alkoxides suspended in absolute ether substitute the cyano group to give the corresponding aminal ester (eq 2). In contrast to the aforementioned method,

Toward a Chemical Constructor: A Lego-Like Approach for Formal α-Alkylation of Cyclic Ketones

“…Previously, we proposed an approach for formal α-methylation of ketones via a convenient two-step protocol. Starting ketones were treated with Bredereck’s reagent or DMF–DMA to yield the corresponding enaminones that were catalytically hydrogenated to α-methyl ketones . The reaction of intermediate enaminones with Li/Mg C-nucleophiles could be used as an alternative to crotonic condensation (Figure , step B).…”