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In a previous report (ref. 5b), we proposed the formation of a
mixture of A and the corresponding polymeric structure from the
reaction between 1b and CO2. However, during the present study,
we noticed that this polymeric structure should be corrected to Aʹ
as shown in Scheme 4. The detailed analytic data as well as
comparison with the DFT-simulated NMR spectra are shown in
the Supporting Information.
Scheme 6. Reaction of 1c with aldehydes 4. Isolated
yields are given.
1
2
3
4
5
6
7
8
9
In conclusion, we developed a synthetic route to
imidic-phosphinic mixed anhydrides and phosphinates via
direct phosphorylation of isocyanates and aldehydes,
respectively,
by
N-phosphine
oxide-substituted
imidazolylidenes (PoxIms). PoxIms served as i)
a
4
5
nucleophile to activate the carbonyl groups in isocyanates
and aldehydes, as well as ii) an electrophile to transfer the
phosphine oxide moieties, which lead to the formation of
the mixed anhydrides and phosphinates. In addition, a
10 PoxIm with bis-N-phosphine oxide groups worked as a
11 catalyst in the cyclotrimerization of phenyl isocyanate. The
12 current study illustrates that strategically designed
13 multifunctional carbene reagents offer unprecedented utility
14 for phosphorylation of carbonyl compounds in organic
15 synthesis.
6
16
This work was supported by Grants-in Aid for Young
17 Scientists (A) (JSPS KAKENHI Grant Number
18 JP25708018), Encouragement for Young Scientists (B)
19 (JSPS KAKENHI Grant Number JP15K17824), and
20 Scientific Research on Innovative Areas “Stimuli-
21 responsive Chemical Species (JSPS KAKENHI Grant
22 Number JP15H00943)” and “Precisely Designed Catalysts
23 with Customized Scaffolding (JSPS KAKENHI Grant
24 Number JP15H05803).” Y.H. acknowledges support from
25 the Frontier Research Base for Global Young Researchers,
26 Osaka University, on the program of MEXT.
7
8
27
28 Supporting
Information
is
available
on
29 http://dx.doi.org/10.1246/cl.******.
30 References and Notes
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1
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114 11 For calculations of the %Vbur values, the following parameters
2
For selected reviews on fuctionalized NHCs, see: (a) S. Hameury,
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were used: sphere radius 3.00 Å; distance for the metal‒ligand
bond 2.00 Å; H atoms were omitted; Bondi radii scaled by 1.17.
These calculations were carried out on the geometrically
optimized structures, that were obtained from DFT calculations