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(-Br-ABCDEF(HABC)2--OTBS) with a more complicated regulated
sequence (Scheme 4a). The uniform nature of 13 was verified by the
presence of single peak and sharp molecular weight distribution in
its SEC trace (Scheme 4b). The observed m/z value (1351.92) of the
expected molecular ion [M+2H]2+ for 13 is consistent with its
theoretical m/z value of 1351.89 (Scheme 4c). 1H NMR spectrum of
13 (Figure S98) also characterized its structure and purity.
There are no conflicts to declare.
DOI: 10.1039/D0CC00421A
Notes and references
1
(a) W.-Q. Fan and A. R. Katritzky, Comprehensive Heterocyclic
Chemistry II, 1996, 4, 1-126; (b) A. C. Tomé, in Science of
Synthesis: Houben-Weyl Methods of Molecular
Transformations, ed. R. C. Storr and T. L. Gillchrist, Thieme,
Stuttgart, 2004, vol. 13, pp. 415-601.
2
3
(a) V. V. Rostovtsev, L. G. Green, V. V. Fokin and K. B.
Sharpless, Angew. Chem., Int. Ed., 2002, 41, 2596; (b) C. W.
Tornøe, C. Christensen and M. Meldal, J. Org. Chem., 2002, 67,
3057.
For selected reviews, see: (a) A. Qin, J. W. Y. Lam and B. Z.
Tang, Chem. Soc. Rev., 2010, 39, 2522; (b) A. Qin, J. W. Y. Lam
and B. Z. Tang, Macromolecules, 2010, 43, 8693; (c) B. Li, D.
Huang, A. Qin and B. Z. Tang, Macromol. Rapid Commun.,
2018, 39, 1800098; (d) Y. Shi, J. Z. Sun and A. Qin, J. Polym. Sci.
Pol. Chem., 2017, 55, 616; (e) B. Yao, J. Z. Sun, A. Qin and B. Z.
Tang, J. Inorg. Organomet. Polym., 2015, 25, 37; (f) M. Juríček,
P. H. J. Kouwer and A. E. Rowan, Chem. Commun., 2011, 47,
8740.
ii. CuAAC
i
a)
6a
6b + 10d
13
(14-mer)
81%
Me
S
O
Ph
Et
Bn
Me
S
Br
S
S
S
N
N
N
N
N
N
N
N
N
N N
N
N
N
N
OTBS
N
N
N
N
N
N
N
N
N
2
N
N
N
N
N
N
H
S
Ph
S
S
S
n-Bu
Me
O
Me
b) SEC traces
13 10d 6b
c) FTICR-MS of 13
[M13+2H]2+
Br
B
C
D
F
H
A
C
H
A
C OTBS
B
A
E
B
4
5
(a) J.-F. Lutz, Polym. Chem., 2010, 1, 55; (b) J.-F. Lutz, M. Ouchi,
D. R. Liu and M. Sawamoto, Science, 2013, 341, 1238149; (c)
J. F. Lutz, T. Y. Meyer, M. Ouchi and M. Sawamoto, Sequence-
controlled polymers: synthesis, self-assembly, and properties;
American Chemical Society, Washington, DC, 2014; (d) J.-F.
Lutz, Sequence-controlled polymers; Wiley-VCH, Weinheim,
2018.
(a) N. G. Angelo and P. S. Arora, J. Am. Chem. Soc., 2005, 127,
17134; (b) S. Pfeifer, Z. Zarafshani, N. Badi and J.-F. Lutz, J. Am.
Chem. Soc., 2009, 131, 9195; (c) T. T. Trinh, L. Oswald, D. Chan-
Seng, L. Charles and J.-F. Lutz, Chem. Eur. J., 2015, 21, 11961.
C. J. Yang, J. P. Flynn and J. Niu, Angew. Chem., Int. Ed., 2018,
57, 16194.
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Acad. Sci. U. S. A., 2015, 112, 10617; (b) J. C. Barnes, D. J. C.
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Jiang, M. R. Golder, H. V.-T. Nguyen, Y. Wang, M. Zhong, J. C.
Barnes, D. J. C. Ehrlich and J. A. Johnson, J. Am. Chem. Soc.,
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Chem. Soc., 2016, 138, 16600; (e) M. R. Golder, Y. Jiang, P. E.
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Scheme 4 Coupling of sequence-defined oligomers. (i) NaN3, DMF, 80 °C;
(ii) CuBr, PMDETA, DMF, 50 °C.
Moreover, to learn the potential applications of sequence-
defined polytriazoles in data storage,16 decoding of 6b was studied
by tandem mass spectrometry (MS/MS). The MS/MS spectra of 6b
(Figure S13) verified the intended sequence of the monomers. Due
to the weak C-S bond in the side chains, peaks involving the
dissociation of one or more side-arms were observed as the majority,
all of which were assigned to the fragments with intended orders,
further confirming the successful synthesis of sequence-defined
polytriazoles (Figure S14).
To sum up, we pioneered the construction of the novel sequence-
defined polytriazole architecture, in which different groups were
anchored at C-5 position of the 1,2,3-triazole rings as side-chains in
regulated sequence. Sequence-regulated macromolecules with up to
~5.3 kDa molecular weight and 31 side groups were smoothly
afforded through IrAAC-based ISG protocol combining with CuAAC-
based IEG strategy and cross-coupling method. Simple reaction
conditions and high yields in these solution-phase processes bring
the opportunity of scalable productions. The identity and purity of
these newly introduced sequence-regulated polymers was
confirmed by characterizations of NMR, SEC, MALDI-MS and FTICR-
MS. Research on the application of this newly introduced skeleton in
different areas is ongoing.
6
7
8
9
N. F. Konig, A. Al Ouahabi, S. Poyer, L. Charles and J.-F. Lutz,
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Z. Huang, Y. Zhou, Z. Wang, Y. Li, W. Zhang, N. Zhou, Z. Zhang
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10 (a) H. C. Kolb and K. B. Sharpless, Drug Discovery Today, 2003,
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11 S. Ding, G. Jia and J. Sun, Angew. Chem. Int. Ed., 2014, 53,
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12 R. B. Merrifield. J. Am. Chem. Soc., 1963, 85, 2149.
13 O. I. Paynter, D. J. Simmonds and M. C. Whiting, J. Chem. Soc.,
Chem. Commun., 1982, 1165.
This work was financially supported by the National Natural
Science Foundation of China (No. 21871023), Big Science Project
from BUCT (XK180301), the Fundamental Research Funds for the
Central Universities (buctrc201719), State Key Laboratory of Natural
and Biomimetic Drugs (Peking University).
14 S. Binauld, D. Damiron, L. A. Connal, C. J. Hawker and E.
Drockenmuller, Macromol. Rapid Commun., 2011, 32, 147.
15 S. Binauld, C. J. Hawker, E. Fleury and E. Drockenmuller,
Angew. Chem., Int. Ed., 2009, 48, 6654.
16 For selected reviews, see: (a) J. F. Lutz, Acc. Chem. Res., 2013,
46, 2696; (b) H. Colquhoun and J. F. Lutz, Nat. Chem., 2014, 6,
455; (c) M. G. T. A. Rutten, F. W. Vaandrager, J. A. A. W.
Elemans and R. J. M. Nolte, Nat. Rev. Chem., 2018, 2, 365.
Conflicts of interest
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