Triethylsiloxymethyl‐N,N‐dimethylamine, Et3SiOCH2NMe2: A Dimethylaminomethylation (Mannich) Reagent for O–H, S–H, P–H and Aromatic C–H Systems

• Published in: European journal of organic chemistry Vol. 2017; no. 37; pp. 5610 - 5616
• Main Authors: Gonzalez, Paulina E., Sharma, Hemant K., Chakrabarty, Sanchita, Metta‐Magaña, Alejandro, Pannell, Keith H.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 10.10.2017; Wiley Subscription Services, Inc
• Subjects: Alcohol; Aliphatic alcohols; Aliphatic compounds; Amination; Chemical synthesis; Chemistry; Chemistry, Organic; Crystal structure; Hydrosilylation; Imminium ions; Mannich reaction; Naphthol; Phosphine oxide; Physical Sciences; Reagents; Science & Technology; Siloxymethylamine; Synthetic methods; Thiols; SELF-ENCAPSULATION; QUINONE METHIDE; COMPLEXES; Imminium ions; TERTIARY; PHOSPHINE OXIDE; Amination; LIGANDS; SECONDARY AMIDES; AMINES; Mannich reaction; Siloxymethylamine; Synthetic methods; CATALYZED REDUCTION; EFFICIENT
• DOI: 10.1002/ejoc.201700902
• ISSN: 1434-193X

Triethylsiloxymethylamine, Et3SiOCH2NMe2, readily synthesized in high yield by the hydrosilylation reaction between Et3SiH and DMF, is an excellent (N,N‐dimethylamino)methyl transfer agent to a representative range of aliphatic alcohols, thiols, and Ph2PH (E–H) materials. The reactions are almost instantaneous at room temperature in inert solvents and require no activating agents to produce E–CH2NMe2 products in high yields and illustrate the title compound as an excellent addition to the family of organic reagents. For aromatic alcohols, electrophilic substitution of the aromatic ring occurs in high yield. Crystal structures of new materials such as the cholestero–CH2NMe2 derivative, 2–4‐[bis(N,N‐dimethylamino)methyl]‐1‐naphthol, and the phosphine oxide derived from Ph2PCH2NMe2 are reported. Triethylsiloxymethyl‐N,N‐dimethylamine, Et3SiOCH2NMe2, prepared in high yield by Mo(CO)6‐catalyzed hydrosilylation of DMF, is an excellent CH2NMe2 transfer agent to OH, SH, and Caromatic–H‐bonded systems, with concomitant formation of Et3SiOH. The transfers occur rapidly under mild conditions, with high recovered yields, and require no activating agents.