Xie Q,
Dong G.
*
University of Chicago, USA
Aza-Matteson Reactions via Controlled Mono- and Double-Methylene Insertions into Nitrogen–Boron
Bonds.
J. Am. Chem. Soc. 2021;
143: 14422-14427
DOI:
10.1021/jacs.1c06186
Key words
aminoboranes - Matteson homologation - methylene insertion - tertiary amines
Significance
In 1963, Donald S. Matteson developed a valuable strategy allowing for carbenoid insertions
into C–B bonds. While this homologation reaction has been thoroughly investigated,
its extension to N–B bonds remained unexplored. The authors describe an aza-Matteson
homologation leading to the selective construction of various α- and β-substituted
amines, which are versatile, synthetically useful building blocks for further transformation.
Comment
Starting from readily accessible aminoboranes, the aza-Matteson reaction provides
access to various α- and β-substituted amines in good yields. By the choice of the
Lewis acid and leaving group attached to the carbenoid, selective mono- or double-methylene
insertion is achieved. The synthetic utility of the method was demonstrated by the
derivatization of biologically active compounds.
