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DBU and TU synergistically induced ring-opening

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polymerization of phosphate esters: a mechanism

Cite this: New J. Chem., 2021,
45, 1953 study†
Shuang Li,a Han Lu,a Xiaohui Kang, ‡*b Pan Wanga and Yi Luo ‡*a

Received 5th November 2020,
Accepted 17th December 2020
DOI: 10.1039/d0nj05422d
rsc.li/njc
Biocompatible and biodegradable polyphosphoesters derived from the ring-opening polymerization (ROP) of
phosphate esters have drawn increasing attention because of their potential applications in clinical and
therapeutic fields. The related knowledge of the ROP mechanism, however, is very limited to date. Herein, the
ROP of 2-isobutoxy-2-oxo-1,3,2-dioxaphospholane (iBP) catalyzed by 1,8-diazabicyclo[5.4.0]undec-7-ene
(DBU) or the combination of DBU/thiourea (TU, 1-[3,5-bis(trifluoromethyl)phenyl]-3-cyclohexylthiourea) was
computationally studied. It is found that DBU plays the roles of both activating BnOH as an initiator and
transporting protons in the two-component DBU/BnOH system. In the three-component (DBU/TU/BnOH)
system, two possible mechanisms, viz., DBU- and TU-induced iBP ring-opening, were explored. In the former
mechanism, DBU acts as a proton relay and TU is an activator of iBP, whereas protonated DBU serves as a
counter cation and TU stabilizes an oxygen-containing anion via hydrogen bond interactions in the latter case.
In comparison, the DBU/TU/BnOH cooperatively catalyzed ROP of iBP is more thermodynamically and
kinetically favorable than that catalyzed by the two-component DBU/BnOH, which could be mainly ascribed
to a more activated P–O bond in iBP by the dual activation role of TU.

Introduction carbene (NHCs),6 and thiourea (TU, 1-[3,5-bis(trifluoromethyl)-

Polyphosphoesters as a novel family of polymers possess great
potential for application in the fields of biology and medicine
because of their excellent biodegradability and biocompatibility,
and thermo-responsibility in aqueous solution.1 Developing effi-
cient synthetic strategies is therefore of great significance. In this
context, ring-opening polymerization (ROP) is often used to
prepare high molecular weight degradable polymers and can
mechanistically offer control over the molecular weights, disper-
sity (Ð), compositions, and structures of polymers.2 To date,
organocatalysts have been extensively used in the ROP of esters
to produce polymeric materials without any metallic residues. The
application of metal-free catalysts in the ROP of cyclic phosphate
esters has also received significant attention.3 Thus far, some
common organic catalysts, viz., 1,8-diazabicyclo[5.4.0]undec-7-ene
(DBU),4 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD),5 N-heterocyclic
phenyl]-3-cyclohexylthiourea)7 derivatives, as shown in Fig. 1(a), were
widely utilized in the ROP of many types of phosphate esters such as
ethyl ethylene phosphate (EEP), 2-isopropoxy-2-oxo-1,3,2-dioxapho-
spholane (iPP), 2-isobutoxy-2-oxo-1,3,2-dioxaphospholane (iBP),
2-methoxy-2-oxo-1,3,2-dioxaphospholane (MP), 2-(but-3-yn-1-yloxy)-
2-oxo-1,3,2-dioxaphospholane (BYP), and 2-ethylbutyl phospholane
(EBP) as shown in Fig. 1(b).
In 2010, Iwasaki firstly reported the ROP of iBP monomer
catalyzed by DBU/BnOH (benzyl alcohol), which is a novel
method for the ROP of cyclic phosphates.8 After that, Wooley’s
group successfully realized the polymerization of the monomer
BYP using the same catalyst at room temperature and obtained
a high molar mass (20 000 g mol 1) polymer of BYP. Beyond
that, the conversion rate can reach 95% in just 6 minutes.2

a
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian
University of Technology, Dalian 116024, China. E-mail: luoyi@dlut.edu.cn
b
College of Pharmacy, Dalian Medical University, Dalian, Liaoning 116044, China.
E-mail: kangxh@dmu.edu.cn
† Electronic supplementary information (ESI) available: Optimized structures,
IRC following of TS1_2A and TS2_3B, the potential energy surface of DBUH+
departure from 2A, NBO analysis, and coordinates of all structures. See DOI:
10.1039/d0nj05422d Fig. 1 Some common organic catalysts (a) and phosphate ester mono-
‡ These two authors contributed equally. mers (b).

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2021 New J. Chem., 2021, 45, 1953--1958 | 1953

Paper
Jérôme’s group also found that the catalytic systems (DBU/
BnOH) and (DBU/TU/BnOH) could both catalyze the ROP of
iBP. In the catalysis using DBU/BnOH, the conversion rate of
iBP could reach 85% within 4 h, while in the case of (DBU/TU/
BnOH) the conversion rate could reach 94% within 40 min,
yielding P(iBP) with a molar mass of up to 70 000 g mol 1, and
the dispersity (Ð) remains mono-modal and narrow.9 They
proposed that DBU activates the initiator BnOH in the DBU/
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BnOH system, while DBU and TU activate BnOH and the
monomer iBP in the DBU/TU/BnOH system. Besides, Waymouth’s
group reported that the co-catalysis of DBU (pKDMSO
a = 13.9) and TU
(pKaDMSO = 13.2) with similar pKa values also showed outstanding
catalytic capacity in the ROP of carbonates.10 However, the detailed
ROP mechanisms including the key geometric structures of transi-
tion states and intermediates and the rate-determining step remain
far from understanding, and the roles of DBU and TU need to be
further revealed.
Some theoretical studies on the organo-catalyzed ROP of
cyclic esters were conducted via DFT calculations.11 During the
ROP of L-lactide (L-LA) mediated by TBD, Rice and co-workers
found that a mechanism involving the hydrogen-bonding inter-
action between TBD and the carbonyl group of L-LA is more
favorable than that of the acetyl transfer of TBD.12 Waymouth’s
group found that the ROP of LA catalyzed by thioureas followed
the mechanism of simultaneous activation of alcohol and LA
via hydrogen-bonding interactions (between thiourea anion
and the alcohol initiator/chain end), thus affecting the selective
ring-opening of lactones and carbonates.13 This reaction
mechanism is closely analogous to that of the TBD system. In
the DFT study of the ROP mechanism of cyclic lactones
catalyzed by TBD, it was found that TBD acts simultaneously
as a proton donor (carbonyl group activation) and as a proton
acceptor (RO–H activation) rather than the intramolecular
acylation of TBD.14 In contrast, computational studies on the
ROP of cyclic phosphate esters catalyzed by organic catalysts
Fig. 2 Energy profiles (distances in Å) of the ROP of iBP catalyzed by (DBU/BnOH). Free energies are relative to isolated reactants.
1954 | New J. Chem., 2021, 45, 1953--1958 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2021
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are rare,15 and related investigations on two-component
systems such as DBU/TU have not been reported so far.
Herein, the ROP mechanism of iBP mediated by DBU/BnOH
or DBU/TU/BnOH has been computationally elucidated. The
purpose of this study is threefold: to explore the ROP mecha-
nism of such two catalytic systems, search key transition states
and intermediates and determine the rate-determining step; to
clarify the role of DBU in the DBU/BnOH mediated reaction;
and to illuminate the roles of TU and DBU in the three-
component DBU/TU/BnOH system. It is expected that the
clarification of these issues could provide valuable information
on the development of more efficient catalysts for the ROP of
phosphate esters.
Computational details
All calculations were performed using the Gaussian 16
program.16 The B3LYP hybrid exchange–correlation func-
tional17 together with the 6-31+G(d,p) basis set for all atoms
was utilized for geometry optimization. At the same level of
theory, frequency analysis was performed to get thermo-
dynamic corrections and also to check whether optimized
structures are minima or saddle points. The transition state
structures are shown to connect the reactant and the product
on either side via intrinsic reaction coordinate (IRC) following.
These structures are optimized in toluene using the CPCM
model.18 To obtain more reliable relative energies, single-point
calculations of optimized structures were carried out at the
B3LYP-D319/6-311+G** level using the CPCM model to consider
the solvation effect of toluene. The aforementioned theoretical
methods were successfully applied to organocatalytic ring-
opening reactions of phosphate esters.20 The 3D molecular
structures displayed in this paper were drawn by using
CYLview.21

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Results and discussion
Two-component DBU/BnOH catalyzed iBP polymerization
It is generally known that the ring-opening polymerization of
cyclic esters includes two steps, viz., nucleophilic attack and
ring-opening.22 As shown in Fig. 2, a ternary complex 1A was
initially formed with an absorption energy of 1.6 kcal mol 1. In
1A, the H–O bond in BnOH and the PQO bond in iBP are
activated by DBU via hydrogen bonds, as indicated by H2


O3
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(2.44 Å) and H1


N (1.75 Å) contacts (Fig. 2 and Fig. S1, ESI†).
Then the BnO group attacks the P1 atom in iBP, accompanied
by the H1 transfer from BnOH to DBU to generate a less stable
intermediate 2A (Fig. S2, ESI†). This step overcomes an energy
barrier (TS1_2A) of 13.9 kcal mol 1. In 2A (Fig. 2), there is
a strong hydrogen bond H1


O3 between DBUH+ and iBP
moieties, as indicated by the stretched P1QO3 (1.54 Å) bond,
the N–H1 bond length (1.08 Å) and a contact of H1


O3 (1.52 Å).
The aforementioned results indicate that DBU initiated the
nucleophilic attack of BnOH, which is consistent with the
speculation of Jérôme’s group.9 It is noted that the dissociation
of protonated DBU from 2A is unlikely to occur since this process
is endergonic by 41.5 kcal mol 1 (Fig. S3, ESI†).
Based on 2A, the proton H1 transfer from BnO to the
endocyclic O atom occurs to generate 3A. These two intermediates
are almost isoenergetic and the transformation between them
takes place more easily in the solution. Next, complex 3A feasibly
overcomes a transition state (TS) TS3_4A to realize the ring-opening
of iBP, accompanied by the formation of O2–H1, yielding a stable
intermediate 4A. This process surmounts an overall energy barrier
of 14.8 kcal mol 1 and releases an energy of 17.2 kcal mol 1. In
TS3_4A (Fig. 2 and Fig. S1, ESI†), double hydrogen bonds exist
as indicated by the distances of H1


O3 (2.15 Å) and H1


O2
(1.86 Å), which were further confirmed by the weak interaction
analysis shown in Fig. 3. The stronger hydrogen bond interaction
of the H1


O2 bond than that of H1


O3 suggests that DBUH+
tends to move from O3 to O2. This indicates that DBU acts as a
proton carrier during the ring-opening process.
With the approach of a new monomer, the ring-opening
product 4A was involved in subsequent chain propagation. As
shown in Fig. 2, beyond the formation of 4A, the chain propaga-
tion undergoes similar nucleophilic attack and ring-opening
Fig. 3 Weak interaction analysis for TS2_3A and TS6_7A using the independent
gradient model (IGM).
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events, featuring the proton transfer by DBU. During the chain
propagation, the energy barriers for the two events were calcu-
lated to be 13.3 and 12.5 kcal mol 1, respectively. In the ring-
opening TS TS6_7A, the hydrogen bond between the protonated
DBU and the O atom in the growing chain (H1


O2 distance of
2.27 Å, Fig. 2 and Fig. S1, ESI†) is different from that in chain
initiation showing the DBU–H


OQP (2.15 Å) interaction
(Fig. 2). Such hydrogen bonds assist in the ring-opening
process. It is obvious that, during the ROP of iBP, DBU plays
a dual role as a proton relay and an activator of BnOH.
Furthermore, such DBU/BnOH mediated ROP of iBP follows
the relay chain-end activation mechanism.23
Besides, the change of NBO charge on DBU from 1A to 7A
(0.07 - 0.38 - 0.07 - 0.07 - 0.07 - 0.42 - 0.06) suggests
that DBU acts as an electron donor in the nucleophilic attack
step and as an electron acceptor in the ring-opening process.
On the basis of the whole energy profile, it was concluded
that the ring-opening in the chain initiation overcomes a
slightly higher energy barrier (14.8 kcal mol 1) than that
(13.5 kcal mol 1) in the chain propagation step, suggesting
the characteristics of slow initiation and fast propagation in the
ROP of iBP mediated by DBU.
Three-component DBU/TU/BnOH catalyzed iBP polymerization
To explore the cooperative catalytic mechanism of DBU and TU,
the polymerization of phosphoesters by the DBU/TU/BnOH
system has been also computationally studied. As shown in
Fig. 4, the monomer involved quaternary complex 1B could be
formed via hydrogen bond interactions, featuring BnO–H bond
activation by DBU and PQO bond activation by TU (via double
hydrogen bonds, Fig. 4 and Fig. S4, ESI†). The BnO group in 1B
could attack the P1 atom in iBP to generate an intermediate 2B
(Fig. S2, ESI†). Such a nucleophilic attack overcomes an energy
barrier of 6.3 kcal mol 1 (TS1_2B), which is lower than that
(13.9 kcal mol 1) in the two-component (DBU/BnOH) system.
This priority in the three-component system might benefit from
the dual activation roles of DBU and TU, as indicated by a
geometrical comparison of TS1_2B and TS1_2A. The P1QO3 bond
(1.48 Å) in TS1_2B elongated to 1.51 Å via double H-bonding with
TU, which was longer than that in TS1_2A (1.50 Å, Fig. 2).
Besides, a more positive NPA charge on the P atom (2.62 vs. 2.59,
Fig. S5, ESI†) in the three-component system also makes the
nucleophilic attack easier.
In 2B, there are two forms of hydrogen atoms, viz., H2/H3 in
TU and H1 in DBUH+, which could induce different modes of
ring-opening of iBP, namely P1–O2 and P1–O4 cleavages. There-
fore, the ring-opening of iBP assisted by DBU or TU was
investigated (Fig. 4).
One pathway is that a proton transferred from DBUH+ to the
O4 atom in iBP and the P1–O4 bond cleavage took place via
TS2_3B to give a more stable intermediate 3B. This step over-
comes an energy barrier of 9.7 kcal mol 1, which is also lower
than that (14.8 kcal mol 1) in the binary DBU/BnOH system.
This discrepancy could be ascribed to the longer P1–O4 bond in
TS2_3B in comparison with the cleaving P–O bond in TS3_4A
(2.29 vs. 1.84 Å, Fig. S1 and S4, ESI†), probably thanks to the
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Fig. 4 Energy profiles of the ROP of iBP catalyzed by (DBU/TU/BnOH), the suffixes ‘‘B’’ and ‘‘C’’ denote the ring-opening pathways assisted by DBU
(black curve) and TU (blue curve), respectively. Free energies are relative to isolated reactants.
dual activation role of TU. Further NBO charge analysis showed
that the charges on the DBU moiety were 0.07 in 1B, 0.43 in 2B,
and 0.08 in 3B (Fig. S6, ESI†). This suggests that DBU still acts
as an electron donor in nucleophilic attack and as an electron
acceptor in the ring-opening process. This situation is the same
as that in the DBU/BnOH binary system, whereas the charges
on TU nearly do not change ( 0.04 in 1B, 0.07 in 2B, and
0.04 in 3B, Fig. S6, ESI†), suggesting that TU just acted as an
activator of iBP.
After the formation of the ring-opening product 3B, the
chain propagation could subsequently occur. As shown in
Fig. 4, the incoming iBP gets inserted into 3B and is activated
by TU via a dual hydrogen bond to produce a more stable
complex 4B. In 4B, the ROH moiety activated by DBU stabilizes
iBP through a weak hydrogen bond interaction (H4


O4
distance of 2.36 Å). Next, the nucleophilic attack takes place
via TS4_5B with an energy barrier of 7.2 kcal mol 1 to yield
intermediate 5B featuring a six-coordinating P atom. The newly
formed 5B could undergo ring-opening, similar to that in chain
initiation. This step has an energy barrier of 11.9 kcal mol 1
(TS5_6B), giving 6B. The whole polymerization process has an
overall energy barrier of 11.9 kcal mol 1 and is exergonic by
13.2 kcal mol 1. The rate-determining step is the ring-opening
at the chain propagation stage. It is obvious that these pro-
cesses are both kinetically and thermodynamically accessible at
room temperature, and the polymerization could smoothly
occur, as observed experimentally.8 During the polymerization,
DBU as a proton relay assisted both nucleophilic attack and
ring-opening processes, while TU acted as an activator of iBP
via double hydrogen bond interactions.
In another pathway, 2B firstly isomerized to a more stable
intermediate 3C through an intramolecular hydrogen bond transfer,
as indicated by the disappearance of the H2


O3 interaction and
1956 | New J. Chem., 2021, 45, 1953--1958 This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2021
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the contact of H2


O2 (1.90 Å). This step overcomes an energy
barrier (TS2_3C) of 5.9 kcal mol 1. In 3C, the P1–O2 bond was
activated by TU via a dual hydrogen bond, as indicated by its
elongation (1.80 Å in 3C and 1.75 Å in 2B, Fig. 4 and Fig. S4, ESI†),
which is beneficial for the ring-opening of iBP. Then, 3C over-
comes TS3_4C to realize iBP ring-opening to produce 4C with an
alkoxyl anion. This step has an energy barrier of 10.2 kcal mol 1
relative to 1B and is endergonic by 6.6 kcal mol 1. The less
stability of 4C could trigger the chain propagation stage by
interacting with the incoming monomer. As shown in Fig. 4,
the O2 atom in 4C bonds directly to the P atom of the incoming
iBP to form 5C. Like the conversion of 2B to 3C, 5C isomerized to
6C via TS5_6C with an energy barrier of 6.8 kcal mol 1. Isomer 6C
could undergo ring-opening via TS6_7C to produce 7C, with an
energy barrier of 7.6 kcal mol 1. Overall, TU induced ring-
opening of iBP overcomes an energy barrier of 10.2 kcal mol 1
and has an energy release of 6.1 kcal mol 1. In this transforma-
tion, TU plays the dual role of activating iBP and stabilizing the
chain-end of alkoxyl anion. Obviously, chain propagation of the
ROP was triggered by the nucleophilic attack of alkoxyl anion.
Conclusions
The ring-opening polymerization of phosphoesters catalyzed by
the two-component DBU/BnOH and the three-component DBU/
TU/BnOH system has been computationally conducted. It has
been found that DBU plays a dual role as a proton relay and as
an activator of BnOH in the binary DBU/BnOH system. In the
ternary DBU/TU/BnOH system, DBU and TU activate BnOH and
iBP in the nucleophilic attack process, respectively. After that,
two possible ring-opening pathways induced by DBU and TU
are found to be accessible. In the DBU induced ring-opening,

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DBU acts as a proton relay, while TU acts as an activator of iBP
via hydrogen bond interactions. In the TU induced ring-opening,
DBU was protonated and then served as a counter cation, while 5 (a) R. C. Pratt, B. G. Lohmeijer, D. A. Long, R. M. Waymouth
TU stabilizes the chain-end alkoxyl anion via dual hydrogen
bond interactions. In both cases, the former is more thermo-
dynamically favorable, while the latter is feasible in kinetics.
Regarding the two types of catalytic systems, the three-
component (DBU/TU/BnOH) mediated ROP of iBP is more
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thermodynamically and kinetically favorable than the ROP
mediated by the binary DBU/TU combination, which was mainly
ascribed to the more activated P–O bond of iBP by the dual
activation role of TU. These findings are expected to provide 6 (a) S. Csihony, D. A. Culkin, A. C. Sentman, A. P. Dove,
useful information for developing new organocatalytic systems
to synthesize biodegradable polymers based on biomass-derived
monomers.
7 A. P. Dove, R. C. Pratt, B. G. Lohmeijer, R. M. Waymouth and
Author contributions
8 Y. Iwasaki and E. Yamaguchi, Macromolecules, 2010, 43,
X. K. and Y. L. conceived and supervised the project. S. L. performed
the quantum chemical calculations and analysed the data. H. L. and
9 B. Clement, B. Grignard, L. Koole, C. Jérôme and
P. W. made key discussions. X. K. and S. L. discussed the data and
wrote the manuscript. All authors approved the final version of the
10
manuscript.
11
Conflicts of interest
12
There are no conflicts of interest to declare.
13
Acknowledgements
14
This work was supported by the NSFC (21674014, 21704011,
U1862115). X. K. thanks the Doctoral Scientific Research Foun-
dation of Liaoning Province China (20180540038). The authors
15
thank the Network and Information Center of Dalian University
of Technology for providing part of the computational
resources.
16
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