Abstract
AbstractThe aminals tetramethylmethylenediamine (TMMDA) la, dicyclohexyldimethylmethylenediamine (CMMDA) lb, and di‐isopropyldimethylmethylenediamine (IMMDA) lc are doubly metalated by LitBu to give LiCH2N(R)CH2N(R)CH2Li [2a: R = Me, 2b: R = Cy (Cy = cyclohexyl), 2c: R = iPr], which precipitate out of pentane as highly pyrophoric substances. Deuteration confirms N‐methyl metalation exclusively. A series of aminomethylation reactions were performed by means of the doubly lithiated aminals 2a‐c. The reactions of 2a‐c with monochlorosilanes yield the silylated species R′3SiCH2MN(R)CH2N(R)CH2SiR′3 (3a: R′= Me, R == Me; 3b: R′ == Me, R == Cy; 3c: R′= Me, R = iPr 4: R′= Ph, R = Me, see Scheme 2). The use of dichlorosilanes lead to six‐membered heterocycles 6a‐6d. 6a is transferred into a mono quarternary ammonium salt 7 by methylation with MeI. The spirocycle 8 is obtained from SiCl4 and two equivalents of 2a. Similarly, several substituted 1,3‐diaza‐5‐phosphacyclohexanes 9a‐e (R1 = Me, Ph, NPh2, NCy2, see Scheme 3) are synthesized by the reaction of dichlorophosphanes R1PC2, with 2a and 2b, respectively. Oxidation of 9d with sulfur yields 12a, which is characterized by X‐ray structure determination.
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