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ChemComm
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COMMUNICATION
Journal Name
Denne, C.‐H. Yang, H. Wang and J. Y. KDaOngI:,1A0.n10g3e9w/C. 9CChCe0m9.4,0I7nEt.
Ed., 2018, 57, 6624; (d) P. Adler, A. Pons, J. Li, J. Heider, B. R.
According to previous studies on the mechanism of the
Atherton–Todd‐type reactions,8‐16 the key intermediates
phosphoryl halides were generated by the nucleophilic attack
of phosphoryl anions on halides. On the basis of the above
experimental observations and previous reports of O2‐initiated
phosphoryl radical reactions,18 a plausible mechanism is
Brutiu and N. Maulide, Angew. Chem., Int. Ed., 2018, 57
,
13330.
7
8
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proposed (Scheme 3). Firstly, P(O)H compound
1 is
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deprotonated by a base (DBU).8‐16 Then, a phosphoryl radical is
generated from the autoxidation of the phosphoryl anion with
O2.18 Phosphoryl chloride might be in situ formed via a chlorine
atom abstraction of CHCl3 by the phosphoryl radical, together
with the formation of a dichloromethyl radical, which might
react with
1 to produce the phosphoryl radical and CH2Cl2.
Afterward, the subsequent nucleophilic substitution reaction
of a nucleophile reagent with phosphoryl chloride affords the
desired product 3 or 5.
9
In summary, we report for the first time the Atherton–Todd‐
type reaction initiated by phosphoryl radicals. Compared with
previous phosphoryl anion‐initiated reactions, this process is
environmentally friendly using open air as the radical initiator
and using less toxic CHCl3 (1 equiv) as the halogenating reagent
without any catalysts and metals being involved. Furthmore,
this protocol occurs under very mild conditions even using
PEG‐200 as the solvent, together with various suitable solvents.
The inexpensive, simple, and efficient synthesis of
phosphinates, phosphinic amides, and phosphoramidates with
high functional‐group tolerance showcases the potential of
this approach in organic synthesis.
10 S. Li, T. Chen, Y. Saga and L.‐B. Han, RSC Adv., 2015, 5, 71544.
11 E. M. Georgiev, J. Kaneti, K. Troev and D. M. Roundhill, J. Am.
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Financial support from the Science and Technology Planning
Project of Guangdong Province (No. 2017A010103044), 100
Young Talents Programme of Guangdong University of
Technology (No. 220413506), and the Open Fund of the Key
Laboratory of Functional Molecular Engineering of Guangdong
Province (No. 2016kf07, South China University of Technology)
is gratefully acknowledged.
14 J. Dhineshkumar and K. R. Prabhu, Org. Lett., 2013, 15, 6062.
15 Q. Chen, J. Zeng, X. Yan, Y. Huang, C. Wen, X. Liu and K.
Zhang, J. Org. Chem., 2016, 81, 10043.
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Pan and J. Han, J. Org. Chem., 2019, 84, 949; (c) Q.‐Y. Li, T. R.
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17 For recent examples, see: (a) J. Ke, Y. Tang, H. Yi, Y. Li, Y.
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Conflicts of interest
There are no conflicts to declare.
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