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length of C(sp)–C(sp) was observed, 2c exhibited the shorter N–
C(sp) and C(sp)–P bond lengths indicating the larger electron-
withdrawing property of Ph2P(O) than Cy2P.
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1
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bromo(phosphoryl)ethyne 1 and diarylamines. Although
ynamines are highly reactive and difficult-to-handle, we
succeeded in the preparation and isolation of phosphoryl
ynamines 2 by utilizing the strong electron-withdrawing
effect of the Ph2P(O) group. The X-ray crystal structure
analysis of 2 showed elongated CC and P=O bonds and
contracted N–C(sp) and C(sp)–P bonds, diagnostic of
iminium-type resonance structure contributions. Phosphoryl
ynamines 2 could be used as aminoethyne equivalent, and
8
9
10 consecutive dephosphorylation and click reaction with azide
11 provided the corresponding 4-amino-1,2,3-triazoles 4 in
12 moderate yields. Further application of phosphoryl ynamine
13 2 to organic synthesis is now under investigation in our
14 laboratory and the results will be disclosed in due course.
15
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This work was supported by a Grant-in-Aid from JSPS
82
17 (JP16H01164 to A.O. and JP19K15574 to Y.O.), JSPS
18 Innovative Areas (JP15K05440 and JP18K05134 to A.O.),
19 Okayama Prefecture Industrial Promotion Foundation
20 (A.O.), Okayama Foundation of Science and Technology
21 (Y.O.), Promotion and Mutual Aid Corporation for Private
22 Schools of Japan (Y.O.) and OUS Research Project (OUS-
23 RP-29-1 to A.O. and Y.O., OUS-RP-19-4 to A.O. and Y.O.).
24 The authors thank Prof. Haruo Yamada, Prof. Kan
25 Wakamatsu of Okayama University of Science and Prof.
26 Hiroki Mori of Okayama University for their useful
27 suggestions, and Research Instruments Center, Okayama
28 University for the measurements of 300 MHz NMR
29 (LA300), 400 MHz NMR (JNM-ECS400 and JNM-
30 ECZ400S) and MALDI-TOF MS (autoflex speed)
31 measurements.
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33 Supporting
34 http://dx.doi.org/10.1246/cl.******.
Information
is
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on
35 References and Notes
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