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ARTICLE
Journal Name
Nucleophilic attack of the Co(I) species on DDT may form the
corresponding alkylated complex. Homolysis of the cobalt–
carbon bond formed a substrate radical.‡‡ Hydrogen radical
Conflicts of interest
There are no conflicts to declare.
DOI: 10.1039/D0CC04274A
2
abstraction should form DDD under N , while an ester or amide
could form in air via acyl chloride intermediate by reaction with
the alcohol or amine, respectively.16
Notes and references
§
[(CN)(H
2
O)Cob(III)6C
1
ester]ClO
4
(Chart S1) was synthesized
by previously reported methods as a regioisomer with several
12
positions of the carboxylic group in the complex. See: B.
Kräutler, C. Caderas, R. Konrat, M. Puchberger and C. Kratky,
Helv. Chim. Acta, 1995, 78, 581-599.
¶
The kinetic traces of positive O.D. at 437 nm and the estimated
kET values are shown in Fig. S8 (ESI†). Though the order of kET
values are similar to those shown in Table1, S/N of data are poor.
Thus we used vales in Table 1 for discussion.
‡
The difference in reactivity between C1 and the C2+P1 system
is dependent on the concentration of i-Pr NEt. The highest 4.4
times increase in reactivity (yield and TON) for C1 was observed
in 0.03 M i-Pr NEt as shown in Table S1 (ESI†).
‡ Spin–trapping experiment by 5,5-dimethyl-1-pyrroline-N-
2
2
‡
oxide (DMPO) supports this mechanism and the reaction was
totally inhibited in the presence of DMPO (entry 11 in Table 2),
which implied a radical pathway for the reaction.
1
2
L. Marzo, S. K. Pagire, O. Reiser and B. König, Angew. Chem.
Int. Ed., 2018, 57, 10034-10072.
(a) M. Parasram and V. Gevorgyan, Chem. Soc. Rev., 2017, 46,
6
227-6240; (b) K. L. Skubi, T. R. Blum and T. P. Yoon, Chem.
Rev., 2016, 116, 10035-10074.
3
(a) L. Chen, Y. Kametani, K. Imamura, T. Abe, Y. Shiota, K.
Yoshizawa, Y. Hisaeda and H. Shimakoshi, Chem. Commun.,
Scheme 1 One-pot syntheses of ester and amide from DDT and
benzotrichloride catalyzed by C1 during visible light irradiation in air.
2
019, 55, 13070-13073; (b) L. Chen, Y. Hisaeda and H.
Shimakoshi, Adv. Synth. Catal., 2019, 361, 2877-2884.
M. E. EI-Khouly, E. EI-Mohsnawy and S. Fukuzumi, J.
Photochem. Photobiol. C: Photochem. Rev., 2017, 31, 36-83.
See reviews: (a) M. Giedyk, K. Goliszewska and D. Gryko,
Chem. Soc. Rev. 2015, 44, 3391-3404; (b) K. Gruber, B. Puffer
and B. Kräutler, Chem. Soc. Rev. 2011, 40, 4346-4363.
H. Shimakoshi and Y. Hisaeda, ChemPlusChem, 2017, 82, 18-
4
5
DDT
1
Cl-
i-Pr2NEt
4
i-Pr2NEt
Cl
-
3
CH OH
6
7
8
9
1
2
9.
B. Steiger, E. Eichenberger and L. Walder, Chimia, 1991, 45,
32-37.
J. Rossier, D. Hauser, E. Kottelat, B. Rothen-Rutishauser and
F. Zobi, Dalton. Trans., 2017, 46, 2159-2164.
T. A. Shell, J. R. Shell, Z. L. Rodgers and D. S. Lawrence,
Angew. Chem. Int. Ed., 2014, 53, 875-878.
Cl
-
CN-
Cl
N
O
2
2
0 (a) N. Boens, V. Leen and W. Dehaen, Chem. Soc. Rev., 2012,
DDD
4
1, 1130-1172; (b) A. Loudet and K. Burgess, Chem. Rev.,
Scheme 2 Proposed mechanism for the catalytic reaction by C1.
2
007, 107, 4891-4932.
1
1 (a) J. Bartelmess, A. J. Francis, K. A. El Roz, F. N. Castellano,
In summary, we have synthesized the B12 complex–BODIPY
dyad by covalent conjunction. The B12 complex worked as an
efficient catalyst for DDT or benzotrichloride transformations
under visible light irradiation. On-going work in our laboratory
W. W. Weare and R. D. Sommer, Inorg. Chem., 2014, 53,
4
527-4534; (b) G.-G. Luo, K. Fang, J.-H. Wu, J.-C. Dai and
Q.-H. Zhao, Phys. Chem. Chem. Phys., 2014, 16, 23884-
3894; (c) G.-G. Luo, K. Fang, J.-H. Wu and J. Mo, Chem.
Commun., 2015, 51, 12361-12364.
2
is focused on the expansion of the BODIPY dye which absorbs 12 Y. Murakami, Y. Hisaeda, T. Ohno, H. Kohno and T.
more long wavelength light to develop a wide ranging utilization
of sunlight in photo-driven organic synthesis.
This study was partially supported by a Grant-in-Aid for
Scientific Research (B) (JP19H02735) from the Japan Society
for the Promotion of Science (JSPS). A part of the study was
performed under the Cooperative Research Program of
Nishioka, J. Chem. Soc. Perkin Trans. 2, 1995, 1175-1183.
3 S. Thakare, P. Stachelek, S. Mula, A. B. More, S.
Chattopadhyay, A. K. Ray, N. Sekar, R. Ziessel and A.
Harriman, Chem. Eur. J., 2016, 22, 14356-14366.
4 M. Fujitsuka, D. W. Cho, S. Tojo, A. Inoue, T. Shiragami, M.
Yasuda and T. Majima, J. Phys. Chem. A. 2007, 111, 10574-
10579.
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1
1
5 M. D. Liptak and T. C. Brunold, J. Am. Chem. Soc., 2006, 128,
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6 H. Tian, H. Shimakoshi, T. Ono and Y. Hisaeda,
ChemPlusChem, 2019, 84, 237-240.
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