Triethylsiloxymethyl‐N,N‐dimethylamine, Et3SiOCH2NMe2: A Dimethylaminomethylation (Mannich) Reagent for O–H, S–H, P–H and Aromatic C–H Systems
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 in...
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Published in | European journal of organic chemistry Vol. 2017; no. 37; pp. 5610 - 5616 |
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Main Authors | , , , , |
Format | Journal Article |
Language | English |
Published |
WEINHEIM
Wiley
10.10.2017
Wiley Subscription Services, Inc |
Subjects | |
Online Access | Get full text |
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Summary: | 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. |
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ISSN: | 1434-193X 1099-0690 |
DOI: | 10.1002/ejoc.201700902 |