Organoboron Derivatives of Stereoregular Phenylcyclosilsesquioxanes

Article abstract of DOI:10.1002/chem.202001676

This study presents the synthesis of organoboron derivatives of stereoregular 4-, 6-, and 12-unit phenylcyclosilsesquioxanes. All compounds obtained were isolated in good yields (70–80 percent) and were fully characterized by ¹H, ¹³C

Full text of DOI:10.1002/chem.202001676

Accepted Article
Accepted Article
Title: Organoboron derivatives of stereoregular
phenylcyclosilsesquioxanes
Authors: Anton Anisimov, Fedor Drozdov, Yulia Vysochinskaya,
Ekaterina Minyaylo, Alexander Peregudov, Fedor Dolgushin,
Olga Shchegolikhina, and Aziz Muzafarov
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
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content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.202001676
Link to VoR: https://doi.org/10.1002/chem.202001676
01/2020

10.1002/chem.202001676
Chemistry - A European Journal
ORGANOBORON DERIVATIVES OF STEREOREGULAR
PHENYLCYCLOSILSESQUIOXANES
Anton A. Anisimov a , Fedor V. Drozdov b , Yulia S. Vysochinskaya a,b, Ekaterina O. Minyaylo a ,
Alexander S. Peregudov a, Fedor M. Dolgushin a,c , Olga I. Shchegolikhina a*, Aziz M. Muzafarov
a,b
a
A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of
Sciences (INEOS RAS) Russia, Moscow, Vavilova St. 28,
b
Enikolopov Institute of Synthetic Polymeric Materials Russian Academy of Sciences
(ISPM RAS), Russia, Moscow
c
Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of
Sciences (IGIC RAS), Russia, Moscow
*olga@ineos.ac.ru
Abstract
This paper presents the synthesis of organoboron derivatives of stereoregular 4-, 6-, and 12-unit
phenylcyclosilsesquioxanes. All the compounds obtained were isolated in good yields (70-80%)
1
and were fully characterized by H, 13C, 29Si, 11B NMR, IR spectroscopy, HRMS ESI, and
elemental microanalysis. The structure of key modifier, obtained for the first time, 4-
(tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) dimethylvinylsilane was also confirmed by single-
crystal XRD.
In the past decade, there has been intense work in the field of synthesizing and studying
the properties of new supramolecular systems.1-4 This motivated by the desire to create new,
unique materials with a given set of properties. The production of such materials became
possible due to the development of modern physicochemical methods of analysis that allow one
to accurately determine the structure of compounds and identify the “structure-property”
relationship.5
Of the wide variety of existing supramolecular systems, three large classes can be
distinguished that differ in the type of bonding: hydrogen-bonded organic frameworks (HOF),6
covalent organic frameworks (COF)7 and metal-organic frameworks (MOF).8 Each of these
supramolecular classes offers promise for various applications.9-15 In this paper, we focus on the
precursors for producing HOFs because such systems are capable of reversible structure
reorganization, which allows one to obtain materials that are sensitive to external effects, which,
in turn, is relevant for the creation of smart materials.16,17
The search for new chemical compounds exhibiting specific interactions is an important
task. Its solution would allow one to obtain materials with specified physical properties that can
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10.1002/chem.202001676
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change depending on certain external effects. From this point of view, organosilicon compounds,
namely siloxane systems, appear to be the most promising objects for solving such problems.
This is due to the wide variety of siloxane forms frameworks and owing to their unique
physicochemical properties.18,19
In the past decade, significant progress has been achieved in the development of new
individual compounds with well-defined spatial structures. It should be noted, that since the
discovery of dendrimers20,21 and molecular brushes,22-24 the field of organosilicon supramolecular
chemistry has undergone a fast evolution due to the advantages of siloxane and carbosilane
structures and the methods for their synthesis. Our group has developed a unique method for
synthesizing functional, stereoregular organosilesesquioxane macrocycles (4, 6 and 12 Si-O
units)25-28 that could not be obtained using classical silicone chemistry methods. This class of
compounds can compete with the currently popular derivatives of calixarenes29 and
cyclodextrins30 in the field of the production of new supramolecular systems.
On the other hand, boric acid derivatives are also intensely studied in order to obtain
supramolecular structures with various architectures, as reflected in review articles by Kubo and
Dichtel.31-33,7 This interest in boric acid derivatives is due to the fact that they can form
intermolecular hydrogen or donor-acceptor bonds and that they easily change their chemical
behavior depending on the environment and the nature of functional groups.34,35 The use of boric
acid derivatives for modifying siloxane polymers proved to be an efficient method for the
production of new materials with various valuable properties. For example, the weak interchain
interactions of B-O or B-N moieties cause formation of a physical network resulting in changes
in the rheological properties of polyborosiloxanes.36 It is worth noting separately that boric acid
derivatives can be selectively bound to natural substrates, for example sugars,37-39 which allows
such molecules to be used as biosensors or specific sorbents.40-42 We assume that combining a
flexible siloxane framework with fragments of boric acid derivatives would allow one to create a
new class of borosiloxane compounds.
In this paper, we present a method for synthesizing new organoboron derivatives of
stereoregular phenylcyclosilsesquioxanes that contain 4, 6, or 12 Si-O units in the structure.
To solve this problem, we synthesized hydride-containing macrocycles 1, 2, and 3 as
siloxane precursors (Figure 1).
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Figure 1. Structures of hydride-containing macrocycles
In order to modify cyclic precursors, compound 6 was synthesized by sequential
substitution of bromine atoms in the starting 1,4-dibromobenzene 4 (Scheme 1). It should be
noted, we previously43 used an organoboron styrene derivative as a modifier incorporated by
means of hydrosilylation. However, the use of this modifier is limited because it is liable to
polymerization and necessitates a multi-stage synthesis. Therefore, for this work we developed
its cheaper and more stable analogue, namely, the organosilicon modifier 6 containing a vinyl
functional group capable of undergoing hydrosilylation.
Scheme 1. Reagents and conditions: i, 1. n-BuLi, THF, -78 °C, then ClSiVin(Me)2; ii,
n-BuLi, THF, -78 °C, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxoborolane (IPTMDOB),
then aqueous 1N HCl.
The structure of compound 6 was also confirmed by single-crystal XRD (the structure
and description see Supporting Information).
The target compounds were synthesized by hydrosilylation in the presence of Karstedt’s
catalyst (Figure 2).
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Figure 2. General scheme for synthesizing the new organoboron derivatives of stereoregular
phenylcyclosilsesquioxanes.
The progress of the reaction was monitored by the disappearance of hydride (Si-H) signals in the
1H NMR spectra. All the compounds obtained were purified by preparative chromatography. As
a result, new organoboron derivatives of stereoregular phenylcyclosilsesquioxanes 7, 8 and 9
were obtained in good yields (70-80%) (Figure 3).
Figure 3. Proposed structures of new organoboron derivatives of stereoregular
phenylcyclosilsesquioxanes.
The new compounds are a viscous liquid in the case of compound 7 and white powders for
compounds 8 and 9. These macrocycles very well soluble in such solvents as dichloromethane,
toluene, benzene, chloroform, THF, hexane, and ethyl acetate.
Thus, we have suggested a simple and convenient method for synthesizing new organoboron
derivatives of stereoregular phenylcyclosilsesquioxanes in high yields. The structure and purity
of all the compounds obtained were confirmed by a set of methods of physicochemical analysis:
13
29
11
1H, C, Si, B NMR, IR spectroscopy, HRMS ESI, and elemental analysis. We intend to use
all the organoboron macrocycle derivatives obtained as precursors for synthesizing new organo-
inorganic hybrid systems. In addition, derivatives of this kind are interesting as macro initiators
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10.1002/chem.202001676
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and as starting compounds for synthesizing macromolecular scaffolds in Suzuki cross-coupling
reactions.
Acknowledgments
This work was supported by the Ministry of Science and Higher Education of the Russian
Federation (Grant of the Government of the Russian Federation No. 14.W03.31.0018)
NMR analysis was performed using the equipment of the Collaborative Access Center “Сenter
for Polymer Research” of ISPM RAS.
The characterization of the compounds obtained was performed with financial support from the
Ministry of Science and Higher Education of the Russian Federation using the equipment of the
Center for molecular composition studies of INEOS RAS (IR and NMR spectroscopy, XRD,
HRMS ESI, elemental analysis).
The synthesis of compounds 1-6 were funded by RFBR according to the research project № 18-
302-00001.
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