Shi Q,
Yang R,
Liu WH *.
Sun Yat-sen University, Guangzhou, P. R. China
Catalytic Reductive Aza-Boron-Wittig Reaction.
ACS Catal. 2025;
15: 3741-3750
DOI:
10.1021/acscatal.4c07896
Keywords
amides - aza-boron-Wittig reaction - iridium catalysis - lactams - vinyl boronates
Significance
The boron-Wittig reaction is a well-established method for synthesizing olefins from
carbonyls and boron-stabilized carbanions. To date, extension of this methodology
to include imines has remained elusive, largely due to the weak bond formed between
boron and nitrogen. The authors herein disclosed a catalytic reductive protocol to
overcome these difficulties, thereby providing the first methodology for an aza-boron-Wittig
reaction.
Comment
The main advantage of the reductive aza-boron-Wittig reaction over a typical boron-Wittig
reaction is the very high observed E/Z selectivity. For instance, benzaldehyde was reacted with 1,1-diborylalkane under
standard boron-Wittig conditions to afford an E/Z ratio of 9.6:1. The same product is formed under the reported conditions with an
E/Z ratio of > 99:1.
