Synthesis of new polyhedral oligomeric silsesquioxane derivatives as some possible antimicrobial agents

Article abstract of DOI:10.1080/10426507.2018.1539721

1,3-Dipolar cycloaddition reactions were studied to synthesize Polyhedral oligomeric silsesquioxane (POSS)-based norbornyl imide derivatives containing izoxazoline groups in good yields. And also 1,3-dipolar cycloaddition reactions of azomethine ylides with POSS-based norbornene dipolarophiles for a synthesis of the novel POSS-based norbornane-fused spiro-1,3-indandionolylpyrrolidines are reported. All newly synthesized POSS compounds were structurally characterized by FTIR, ¹H, ¹³C NMR, HRMS and GC/MS analyses.

Full text of DOI:10.1080/10426507.2018.1539721

Phosphorus, Sulfur, and Silicon and the Related Elements
ISSN: 1042-6507 (Print) 1563-5325 (Online) Journal homepage: https://www.tandfonline.com/loi/gpss20
Synthesis of new polyhedral oligomeric
silsesquioxane derivatives as some possible
antimicrobial agents
Elif Basak Ersoy, Omer Tahir Gunkara & Nuket Ocal
To cite this article: Elif Basak Ersoy, Omer Tahir Gunkara & Nuket Ocal (2019) Synthesis of
new polyhedral oligomeric silsesquioxane derivatives as some possible antimicrobial agents,
Phosphorus, Sulfur, and Silicon and the Related Elements, 194:3, 257-268
To link to this article: https://doi.org/10.1080/10426507.2018.1539721
View supplementary material
Published online: 09 Jan 2019.
Submit your article to this journal
Article views: 32
View Crossmark data
Citing articles: 1 View citing articles
Full Terms & Conditions of access and use can be found at
https://www.tandfonline.com/action/journalInformation?journalCode=gpss20

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
2019, VOL. 194, NO. 3, 257–268
https://doi.org/10.1080/10426507.2018.1539721
Synthesis of new polyhedral oligomeric silsesquioxane derivatives as some
possible antimicrobial agents
Elif Basak Ersoy , Omer Tahir Gunkara , and Nuket Ocal
Faculty of Science and Arts Chemistry Department, Yildiz Technical University, Istanbul, Turkey
ABSTRACT
ARTICLE HISTORY
Received 1 August 2018
Accepted 19 October 2018
1,3-Dipolar cycloaddition reactions were studied to synthesize Polyhedral oligomeric silsesquioxane
(POSS)-based norbornyl imide derivatives containing izoxazoline groups in good yields. And also
1,3-dipolar cycloaddition reactions of azomethine ylides with POSS-based norbornene dipolaro-
philes for a synthesis of the novel POSS-based norbornane-fused spiro-1,3-indandionolylpyrroli-
dines are reported. All newly synthesized POSS compounds were structurally characterized by
KEYWORDS
1,3-Dipolar cycloaddition;
azomethine ylide; coating
material; polysiloxanes;
polyhedral oligomeric
silsesquioxane (POSS)
1
FTIR, H, 13C NMR, HRMS and GC/MS analyses.
GRAPHICAL ABSTRACT
Introduction
groups on the silsesquioxane and that enhances the compati-
bility of POSS with many polymers.[11]
The silsesquioxane topic has been known for more than a
century, but interest in this field has increased enormously
within the recent decades.[1,2] Polyhedral oligomeric silses-
quioxane (POSS) is a hybrid organic-inorganic material and
its chemical structure is in between silica (SiO2) and sili-
cones (R2SiO).[3] This all-purpose well-defined nanostruc-
ture possesses a three-dimensional rigid inorganic silica
cage, with the formula of Si8O12, surrounded by 8 different
organic functional groups (Figure 1).[4,5]
Silsesquioxane can be conveniently incorporated into a
polymer system by either physical mixing or a chemical
reaction to get original polymer hybrids.[6] Great numbers
of hybrid materials such as polymeric nanocomposites with
POSS core have recently been developed.[12–17]
During the last decade, more and more attention has
focused on novel architectures of POSS-containing
hybrid polymers.[18]
The incorporation of POSS moieties into a polymer
matrix can significantly enhance its mechanical specifica-
tions, showed an improvement of reduced flammability, oxi-
dation resistance, heat-evolution features, and viscosity
during processing.[3,19–26]
Unlike conventional organic compounds, POSS molecules
are odorless, nonvolatile and eco-friendly.[6]
The most important characteristic of silsesquioxane lies
within their molecular scale (their diameter is approximately
1.5 nm). POSS derivatives have received wide-range of inter-
ests[6–9] due to their perfectly defined chemical structure
and good functionalization flexibility.[10]
Furthermore, it should be pointed out that there is a
remarkable interest in the development of antimicrobial
agents and surfaces for applications in the food packaging,
It is possible to produce numerous varied characteristic
POSS-based structures by altering the size and functional medical industry, and hygiene industry.[27–31]
CONTACT Omer Tahir Gunkara
gunkara@yildiz.edu.tr
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpss.
Supplemental data for this article can be accessed here.
ß 2018 Taylor & Francis Group, LLC

258
E. B. ERSOY ET AL.
Figure 1. POSS Structure.
Scheme 1. Synthesis of compounds 2a–c.
Treatment of compounds 2a-c with oxalyl chloride in dry
dichloromethane gave the 2-(4-Azabicyclo[2.2.1]hept-8-ene-
3-endo,5-endo-dicarboximide-4-yl) propionyl chloride (3a),
2-(4-Azabicyclo[2.2.1]hept-8-ene-3-endo,5-endo-dicarboximide-
4-yl)-3-phenyl propionyl chloride (3b) and 2-(4-
Azabicyclo[2.2.1]hept-8-ene-3-endo,5-endo-dicarboximide-4-
yl)-3-methyl pentanoyl chloride (3c) in 95, 98 and 94%
yields, respectively. We have synthesized 3c on our another
work.[46] (Scheme 2).
Figure 2. Designed POSS molecules.
The structures of all new acyl chloride derivatives have
1
been confirmed by FTIR, H, 13C NMR and LC-MSMS/Qtof
The antimicrobial coatings should combine the desired
properties such as potent antibacterial activity, eco-friendli-
ness, low toxicity and ease of manufacture.[28–35]
Having this in mind, we focused on the development of
some antimicrobial coating agents. POSS-based structures
have great potential for easily incorporated into a polymer
system, and may them use as an antimicrobial coating mate-
rials. Because of this possible use, we designed some novel
analyses. Having studied the infrared spectra of the acyl
chloride compounds 3a–c, the carboxylic acid hydroxy
group OH peak in the spectrum of acid compound observed
at 3300 cmꢀ1 was completely lost in the acyl chloride deriva-
tives. The mass spectra of all the acyl chloride derivatives
3a–c showed the molecular ion peak [M]þ.
Treatment of the aminopropyl isobutyl POSS with the
POSS derivatives which have got izoxazoline or spiro-1,3- acyl chloride derivatives (3a–c) in dry CH2Cl2 at room tem-
perature under nitrogen atmosphere afforded the condensa-
tion amide products (4a–c) in 80, 79 and 90% yields,
respectively (Scheme 3).
indandionolyl pyrrolidine ring system on their structures
(Figure 2). We selected these groups because of their anti-
microbial activity potentials.[36–38]
The spectroscopic data of POSS derivatives 4a–c are
given in detail in the Experimental part. All newly synthe-
sized POSS derivatives confirmed on the basis of their spec-
troscopic data. For compounds 4a–c, the LC-MSMS/Qtof
spectra displayed the correct molecular ion peaks (Mþ.) in
accordance with the proposed structures. Their FT-IR spec-
Izoxazoline and spiro-1,3-indandionolyl pyrrolidine
groups have also evoked considerable interest in organic
synthesis due to their promising biological activities.[39–43]
In view of this, it was of considerable interest to synthe-
size the desired POSS-based compounds with the hope of
obtaining potent antimicrobial active molecules which may
be used in the polymer matrix.
tra showed amide NH peaks at 3333, 3301 and 3340 cmꢀ1
,
respectively. These NH peaks demonstrate that the conden-
sation has occurred and the amide bond is formed. POSS
cage group Si–O–Si characteristic stretching vibration
observed at 1537, 1551 and 1524 cmꢀ1, respectively. The
bands appeared at 1085 cmꢀ1 for 4a, 1084 cmꢀ1 for 4b and
1083 cmꢀ1 for 4c due to vibrations of the O–Si–R bond.
Antimicrobial coating studies for the new compounds
can be carried out in advanced applications.
Results and discussion
1
Bicyclo-[2.2.1]hept-5-ene-endo,endo-2,3-di-carboxylic anhyd-
ride (endic anhydride) 1 was obtained from the reaction
between maleic anhydride and freshly distilled cyclopenta-
diene with a known procedure.[44]
Optically active norbornenylimide substituted amino
acids 2a-c were obtained from 1 with L-amino acids (L-ala-
nine, L-phenyl alanine or L-isoleucine), respectively, using a
known procedure[45] (Scheme 1).
Their H NMR spectra exhibited all the signals of the sug-
1
gested structures. In the H-NMR spectra, the compounds
4a–c gave a doublet of doublets at 0.60, 0.52 and 0.58 ppm,
respectively due to its CH2–Si protons at the seven isopropyl
side chain. Isopropyl methyl protons appeared as a doublet
at 0.95 ppm for 4a, a doublet of doublet at 0.88 ppm for 4b
and a doublet at 0.94 for 4c. The NH protons appeared as a
broad singlet at 5.86, 5.88 and 6.83 ppm respectively.

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
259
Scheme 2. Synthesis of compounds 3a–c.
Scheme 3. Synthesis of compounds 4a–c.
Scheme 4. Synthesis of compounds 5a–c.
Also ¼ C–H protons appeared as a broad singlet at 6.14 ppm the most convenient and attractive route is probably the 1,3-
for 4a, appeared as a doublet of doublet at 5.73 and dipolar cycloaddition of nitrile oxides to alkenes.
Unfortunately, the 1,3-dipolar cycloaddition reaction with
5.81 ppm for 4b and appeared as a doublet at 6.07 and
6.11 ppm for 4c.
4-bromobenzaldehyde oxime[47] and 4a–c gave 5a–c with
The 1,3-dipolar cycloaddition reactions of POSS deriva- low yields. Then, 4-Bromo-N-hydroxybenzenecarboximidoyl
tives were investigated. A variety of synthetic methods has chloride was obtained[48] and used as a starting material for
been developed for the preparation of isoxazolines, of which the 1,3-dipolar cycloaddition reaction. Reaction with 4-

260
E. B. ERSOY ET AL.
Scheme 5. Synthesis of compounds 6a and 6b.
Bromo-N-hydroxybenzenecarboximidoyl chloride and N-[3-
N-Hydroxy-2-thiophenecarboximidoyl chloride[66] was
(isobutylpolyhedral oligomeric silsesquioxanyl)propyl]-2-(4- also a compatible substrate, performing the 1,3-dipolar
Azabicyclo[2.2.1]hept-8-ene-3-endo,5-endo-dicarboximide-4-
cycloaddition reaction with Trisnorbornenylisobutyl POSS to
yl) propanamide (4a), N-[3-(isobutylpolyhedral oligomeric afford the corresponding product 7a and 7b in 32 and 35%
silsesquioxanyl)propyl]-2-(4-Azabicyclo[2.2.1]hept-8-ene-3-
endo,5-endo-dicarboximide-4-yl)-3-phenyl propanamide (4b)
or N-[3-(isobutylpolyhedral oligomeric silsesquioxanyl)-
propyl]-2-(4-Azabicyclo[2.2.1]hept-8-ene-3-endo,5-endo-
dicarboximide-4-yl)-3-methyl pentanamide (4c) pro-
ceeded smoothly to offer 5a-c in 75, 65 and 84% yields,
respectively (Scheme 4).
yields (Scheme 6).
The characteristic data of compounds 5a–c, 6a–b and
7a–b are given in detail in the Experimental part.
Interestingly, Trisnorbornenyl isobutyl POSS reacted with
N-Hydroxy-2-thiophenecarboximidoyl chloride only one
norbornenyl alkenic bond affording the compound 7a
and 7b.
Although three equivalent N-Hydroxy-2-thiophenecar-
boximidoyl chlorides were used for this reaction, all norbor-
nenyl alkenic bonds weren’t reacted with nitrile oxide
Cycloaddition reaction with 4-Bromo-N-hydroxybenzene-
carboximidoyl chloride and Norbornenylethylisobutyl POSS
was also effective, delivering 6a and 6b in 35 and 40% yields
(Scheme 5). The cycloadditions were found to be completely
stereoselective, giving only the exo cycloadducts in moderate
to good yields.
1
reactant. 7a and 7b have been characterized by FTIR, H,
1
13C NMR and TOF/Qtof analyses. Their H NMR spectra
exhibited all the signals of the suggested structures. In the
1H NMR spectra, the compound 7a gave a doublet of dou-
blets at 5.88 ppm and a doublet of doublets at 6.09 ppm due
to its four ¼ C–H protons at the 2 norbornenyl alkene
bonds. Similarly, the compound 7b gave doublet of doublet
at 5.89 ppm and at 6.09 ppm due to its four ¼ C–H protons
at the 2 norbornenyl alkene bonds. The central norbornene
alkene bond should be reacted with N-Hydroxy-2-thiophe-
necarboximidoyl chloride, because there is symmetry within
Previous examples in the literature have shown that the
1,3-dipolar cycloaddition reactions with norbornene and
norbornadiene derivatives proceed on the exo face (with
respect to the methylene bridge).[49–52] In the 1,3-dipolar
cycloaddition reactions of oxabicyclo [2,2,1] heptadiene sys-
tems also, exo-rule prevails.[53–60] Moreover, unsymmetric-
ally substituted norbornenes and norbornadienes have been
reported to undergo cycloaddition reactions with complete
stereoselectively.[61–64]
1
their H NMR spectra.
Tajabadi et al. work[65] showed that exo ring systems are
preferred because of the lower distortion of strained dipolar-
ophiles and the lower torsional effects, present in the related
And also 1,3-dipolar cycloaddition reactions of azome-
thine ylide with POSS derivatives were investigated.
The 1,3-dipolar cycloaddition of azomethine ylides with
TSs. Among the exo transition states, anti regioisomers are electron-deficient olefins is an outstanding method for the
more stable than syn ones because of the lower distortion enantio- and stereoselective synthesis of highly functional-
and more favorable interactions. The calculated population ized pyrrolidines.
Babu procedure[60] has led to the synthesis of a new class
of products, based on the Gibbs energy of transition states,
of norbornane-fused spiro-1,3-indandionolylpyrrolidines
reflects the experimental findings.
Only adducts to the norbornene system were formed having a fascinating architecture consisting of an array of
with a complete site-selectivity and exo selectivity which was stereocenters with an excellent degree of stereocontrol. With
proved by coupling pattern of H6 and H7 in the 1H an ethanol and 1,4-dioxane solvent system, only exo- ring
NMR spectra.
system obtained.

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
261
Scheme 6. Synthesis of compounds 7a and 7b.
Scheme 7. Preparation of compound 8.
We studied the reaction of 8 with in situ generated azo-
Pleasingly, Trisnorbornenyl isobutyl POSS reacted well
methine ylides from ninhydrin and sarcosine in various sol- with the azomethine ylide in ethanol and 1,4-dioxane (1:1
vents, toluene, methanol, 1,4-dioxane, and acetonitrile. ratio) for 24 h afforded the corresponding product 9 in 57%
Ethanol/1,4-Dioxane system was found to be the best in yield (Scheme 8).
terms of yield and regio-, and stereoselectivity.
Similarly, Trisnorbornenyl isobutyl POSS reacted with
The reaction of Norbornenylethyl isobutyl POSS with azomethine ylide only one norbornenyl alkene bond
azomethine ylide prepared from ninhydrine and sarcosine affording the compound 9. In our experiments, we per-
gave the product 8 in good yield as an expected spiro-1,3- formed the reactions with 1:1, 1:2 and 1:3 ratios of
indandiolylpyrrolidine derivative (Scheme 7).
Trisnorbornenyl isobutyl POSS with the reactants

262
E. B. ERSOY ET AL.
Scheme 8. Preparation of compound 9.
obtaining compound
9
as
a
single diastereomer in silica gel GF 254 was used to monitor reaction progress and
also plates were visualized by exposure to UV light, KMnO4
each case.
1
Its H NMR spectra exhibited all the signals of the sug-
gested structure. And also the HRMS spectrum displayed
the correct molecular ion peaks (Mþ.) in accordance with
the proposed structure.
or Vanillin stain. Gallenkamp digital thermometer was used
to determine melting points of all solid compounds. IR spec-
tra were recorded on a Perkin Elmer FT-IR spectrometer.
1H and 13C NMR spectra were obtained with a Bruker
Avance III-500 MHz NMR system. Chemical shifts were
reported in parts per million (ppm) with respect to internal
standard TMS. Data are reported as follows: chemical shift,
multiplicity (s ¼ singlet, d ¼ doublet, t ¼ triplet, q ¼ quartet,
br ¼ broad, m ¼ multiplet, dd ¼ doublet of doublet,
dt ¼ doublet of triplet, p ¼ pentet, hept ¼ heptet), coupling
constants (Hz), number of protons. Mass spectral studies
were performed on an Agilent 6890N/5973 GC/IMSD sys-
tem and high-resolution mass spectra were recorded on an
Agilent G6530B TOF/Qtof Mass spectrometer. All crude
products were purified with Teledyne Isco CombiFlash Rf
200 system and RediSep Rf Gold Silica columns.
Conclusions
In conclusion, we reported an efficient synthetic strategy for
the preparation of new 12 POSS norbornenyl derivatives.
These newly synthesized POSS-based derivatives should have
the potential to show several antimicrobial activities due to
their chemical structure which contains amino acid side
chains, izoxazoline or spiro-1,3-indandionolyl pyrrolidine
groups. And also we synthesized 2 new norbornenyl acyl
chloride derivatives for use as a starting material. The struc-
tures of the new derivatives were characterized by their
spectroscopic data such as FTIR, H NMR, 13C NMR, LC-
1
MSMS/QTOF and GC-MS analyses.
General procedure for the synthesis of norbornyl imide
acyl chloride derivatives (3a–c)
Experimental
A solution of oxalyl chloride (507 mg, 4.00 mmol) in dry
dichloromethane (10 mL) was added dropwise L-amino acid
derivatives (2a–c) (2.00 mmol) in dry dichloromethane
(10 mL) at room temperature under nitrogen atmosphere.
The reaction mixture was stirred at room temperature. After
the TLC control, the solvent was evaporated and the the
leftover residue was washed with diethyl ether. Acyl chloride
derivatives (3a–c) were obtained in almost quantita-
General
Aminopropyl isobutyl POSS, Norbornenylethyl isobutyl
POSS and Trisnorbornenylisobutyl POSS were purchased
from Hybrid Plastic. L-alanine, L-phenyl alanine and L-iso-
leucine were purchased from Alfa Aesar. Other reactant or
reagents were purchased from Sigma Aldrich or Merck and
without further treatment. The solvents were dried by
known techniques. Thin-layer chromatography (TLC) on tive yields.

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
263
2 -(4-Azabicyclo[2.2.1]hept-8-ene-3-endo,5-endo-
dicarboximide-4-yl) propionyl chloride (3a)
6.93, CH2-Si); 0.95 (42H, d, J ¼ 6.62, CH3); 1.46 (3H, d,
J ¼ 7.56, CH3); 1.54–1.57 (3H, m, CH2 and Ha); 1.75 (1H,
dt, J ¼ 1.57; 10.4, Hs); 1.81–1.87 (7H, m, CH); 3.18–3.23
(2H, m, CH); 3.30 (2H, dd, J ¼ 4.09; 5.67, CH); 3.42 (2H,
brs, CH); 4.58 (1H, q, J ¼ 7.25, CH); 5.86 (1H, brs, NH);
6.14 (2H, brs, =CH). 13C NMR (125 MHz, CDCl3), d, ppm:
9.49 (CH2); 14.5 (CH3); 22.4 (7xCH2); 22.8 (CH2); 23.8
(7xCH); 25.7 (14xCH3); 42.2 (CH2); 45.1 (CH); 45.2 (CH);
45.6 (CH); 45.7 (CH); 49.8 (CH); 52.3 (CH2); 134.6 (CH);
134.9 (CH); 168.3 (C ¼ O); 177.0 (C ¼ O); 177.1 (C ¼ O).
HRMS: - Found, m/z: 1091.300 [M]þ. C43H82N2O15Si8.
Calculated, m/z: 1090.3869.
Colorless oil; Yield: 95%; IR: ꢀ cmꢀ1 2983, 2942, 2921 and
2873 (Aliphatic CH), 1773, 1736 and 1694 (C ¼ O), 1453,
1
1377. H NMR (500 MHz, CDCl3), d, ppm (J, Hz): 1.39 (3H,
d, J ¼ 7.25, CH3); 1.52 (1H, d, J ¼ 8.82, H10a); 1.72 (1H, d,
J ¼ 8.82, H10s); 2.89 (1H, s, H1); 2.98 (1H, s, H7); 3.28 (1H,
dd, J ¼ 4.09; 8.51, H2); 3.38–3.40 (1H, m, H6); 4.59 (1H, q,
J ¼ 7.25, CH); 6.09 (2H, brs, =CH). 13C NMR (125 MHz,
CDCl3), d, ppm: 14.5 (CH3); 45.2 (CH); 45.7 (CH); 45.9
(CH); 46.2 (CH); 47.5 (CH); 52.2 (CH2); 134.4 (=CH); 134.5
(=CH); 169.7 (C ¼ O); 176.6 (C ¼ O); 176.7 (C ¼ O). HRMS:
-
Found, m/z: 254.9000 [M þ H]þ. C12H12ClNO3.
N-[3-(isobutylpolyhedral oligomeric
silsesquioxanyl)propyl]-2-(4-Azabicyclo[2.2.1]hept-8-ene-
3-endo,5-endo-dicarboximide-4-yl)-3-phenyl
propanamide (4b)
Calculated, m/z: 253.0506.
2 -(4-Azabicyclo[2.2.1]hept-8-ene-3-endo,5-endo-
dicarboximide-4-yl)-3-phenyl propionyl chloride (3b)
White Solid. m.p.: 139–142 ꢁC. Yield: 80%. IR: ꢀ cmꢀ1 3301
(NH), 2952, 2926, 2906 and 2869 (Aliphatic CH), 1699
(C ¼ O), 1551 (Si–O–Si), 1463, 1383, 1366, 1084 (O–Si–R).
1H NMR (500 MHz, CDCl3), d, ppm (J, Hz): 0.47–0.50 (2H,
m, CH2–Si); 0.52 (14H, dd, J ¼ 3.46; 6.93, CH2–Si); 0.88
(42H, dd, J ¼ 1.89; 6.62, CH3); 1.38 (1H, d, J ¼ 8.82, H10a);
1.46–1.52 (4H, m, CH2); 1.58 (1H, d, J ¼ 8.82, H10s); 1.75
(7H, hept, J ¼ 3.46, CH); 2.95 (1H, dd, J ¼ 4.41; 7.88, CH2);
3.06 (1H, dd, J ¼ 4.41; 7.88, CH2); 3.14 (2H, t, J ¼ 7.88,
CH2); 3.28 (1H, brs, H1); 3.21 (1H, brs, H7); 3.29-3.36 (2H,
m, H2, H6); 4.77 (1H, dd, J ¼ 6.30; 10.71, CH); 5.73 (1H, dd,
J ¼ 2.83; 5.67, CH); 5.81 (1H, dd, J ¼ 2.83; 5.67, CH); 5.88
(1H, brs, NH); 7.05 (2H, d, J ¼ 7.25, ArH), 7.11–7.18 (3H,
m, ArH). 13C NMR (125 MHz, CDCl3), d, ppm: 9.5 (CH2);
22.5 (CH2x7); 23.8 (CHx7); 25.7 (CH3x14); 33.9 (CH2); 42.2
(CH2); 44.9 (CH); 45.0 (CH); 45.5 (CH); 52.4 (CH2); 55.8
(CH); 127.0 (CAr); 128.4 (CAr); 128.6 (CAr); 129.0 (CAr);
134.7 (CAr); 136.7 (Cq); 167.8 (C ¼ O); 177.1 (C ¼ O); 177.4
Brown oil; Yield: 98%; IR: ꢀ cmꢀ1 3064 and 3028 (Aromatic
CH), 2989, 2942 and 2872 (Aliphatic CH), 1793 and 1703
1
(C ¼ O), 1497, 1455, 1378, 725. H NMR (500 MHz, CDCl3),
d, ppm (J, Hz): 1.42 (1H, d, J ¼ 8.82 Hz, H10a); 1.59 (1H, d,
J ¼ 8.82, H10s); 2.95 (1H, s, H1), 3.10 (1H, d, J ¼ 4.72, H7);
3.24 (2H, brs, CH2); 3.34 (1H, dd, J ¼ 3.15; 14.5, H2), 3.46
(1H, dd, J ¼ 5.35; 15.1, H6); 5.01 (1H, dd, J ¼ 5.35; 11.6,
CH); 5.46 (1H, dd, J ¼ 3.15; 5.67, =CH); 5.71 (1H, dd,
J ¼ 3.15; 5.67, =CH); 7.10–7.14 (2H, m, ArH); 7.24–7.27
(3H, m, ArH). 13C NMR (125 MHz, CDCl3), d, ppm: 33.65
(CH2); 44.66 (CH); 44.93 (CH); 45.72 (CH); 45.91 (CH);
52.18 (CH2); 52.60 (CH); 126.95 (CAr); 128.44 (CAr x2);
129.09 (CAr x2); 134.31 (=CH); 134.14 (=CH); 136.36 (Cq);
172.72 (C ¼ O); 177.05 (C ¼ O); 177.12 (C ¼ O). HRMS: -
Found, m/z: 329.1820 [M]þ. C18H16ClNO3. Calculated, m/
z: 329.0819.
(C ¼ O). HRMS:
-
Found, m/z: (z ¼ 2): 584.2236
General procedure for the synthesis of POSS-based
amide derivatives (4a–c)
[M þ 2H]þþ2, 606.6932 [M þ 2Na] þ 2. C49H86N2O15Si8.
Calculated, m/z: 1166.4182.
A solution of norbonyl imide acyl chloride derivatives
(3a–c) (1.00 mmol) in dry dichloromethane (5 mL) was
added to solution of aminopropyl isobutyl POSS (874.58mg,
1.00 mmol) in dry dichloromethane (5 mL) at room tem-
perature under nitrogen atmosphere. The reaction mixture
was stirred for 10h–24h (depending on TLC monitor) at
room temperature. The reaction mixture was concentrated
under reduced pressure, the crude product was subsequently
purified through combiflash chromatography to yield the
desired products.
N-[3-(isobutylpolyhedral oligomeric
silsesquioxanyl)propyl]-2-(4-Azabicyclo[2.2.1]hept-8-ene-
3-endo,5-endo-dicarboximide-4-yl)-3-methyl
pentanamide (4c)
White Solid; mp 137–139 ꢁC; Yield: 90%. IR: ꢀ cmꢀ1 3340
(NH), 2953, 2930, 2906 and 2870 (Aliphatic C–H), 1690
(C ¼ O), 1083 (O–Si–R), 1524 (Si–O–Si), 1463, 1398, 1382,
1
1038 (C–N), 878. H NMR (500 MHz, CDCl3), d, ppm (J,
Hz): 0.58 (14H, dd, J ¼ 2.20; 6.93, CH2–Si); 0.79 (3H, t,
J ¼ 7.25, CH3); 0.90–0.99 (2H, m, CH2); 0.94 (42H, d,
J ¼ 6.62, CH3); 1.24–1.30 (1H, m, CH2); 1.51–1.57 (3H, m,
CH2, H10a); 1.74 (1H, d, J ¼ 8.82, H10s); 2.47–2.53 (1H, m,
CH); 1.84 (7H, hept, J ¼ 4.41, CH); 3.10–3.15 (1H, m, H2);
3.18–3.23 (1H, m, H6); 3.27–3.31 (2H, m, N–CH2); 3.40
(2H, brs, H1, H7); 4.1 (1H, d, J ¼ 11.6, CH); 6.07 (1H, d,
N-[3-(isobutylpolyhedral oligomeric
silsesquioxanyl)propyl]-2-(4-Azabicyclo[2.2.1]hept-8-ene-
3-endo,5-endo-dicarboximide-4-yl) propanamide (4a)
White solid. m.p.: 167–169 ꢁC. Yield: 80%. IR: ꢀ cmꢀ1 3333
(NH), 2952 and 2870 (Aliphatic CH), 1704 (C ¼ O), 1537
(Si–O–Si), 1463, 1381, 1366, 1085 (O–Si–R). 1H NMR J ¼ 2.83, =CH); 6.11 (1H, d, J ¼ 2.83, =CH); 6.83 (1H, brs,
(500 MHz, CDCl3), d, ppm (J, Hz): 0.60 (16H, dd, J ¼ 1.89; NH). 13C NMR (125 MHz, CDCl3), d, ppm: 9.6 (CH2); 9.9

264
E. B. ERSOY ET AL.
(CH3); 15.6 (CH3); 22.5 (CH2); 23.0 (CH2); 23.9 (CHx7); CH2); 0.61 (14 H, t, J = 6.93, 7xCH2–Si); 0.82–0.93 (2H, m,
23.9 (CH); 25.3 (CH2x7); 25.7 (CH3x14); 31.9 (CH); 41.9 CH2); 0.95 (42H, dd, J = 3.15; 6.62, 14xCH3); 1.43 (1H, d,
(CH2); 45.2 (CH); 45.5 (CH); 45.7 (CH); 52.4 (CH2); 62.4 J = 11.35, CH); 1.57–1.67 (3H, m, H10a, H10s, CH); 1.82 (7H,
(CH); 134.7 (=CH); 134.8 (=CH); 168.6 (C ¼ O); 178.0 pent, J = 6.62, 7xCH); 2.73 (1H, dd, J = 4.72; 19.86, H1);
(C ¼ O); 178.2 (C ¼ O). HRMS: - Found, m/z: (z ¼ 2)
2.99–3.11 (3H, m, CH2, H7); 3.22–3.33 (2H, m, N–CH2);
568.2034
[C46H88N2O15Si8] þ 2,
606.6390
3.37–3.44 (1H, m, H9n); 3.54 (1H, dd, J ¼ 11.98; 14.18, H8n),
4.06 (1H, m, CH); 5.94 (1H, s, NH), 6.92 (1H, t, J = 7.25,
ArH); 7.15 (3H, dd, J = 7.88; 15.44, ArH); 7.25 (1H, d,
J = 5.99, ArH); 7.36 (1H, d, J = 8.51, ArH); 7.43 (1H, d,
J = 8.51, ArH); 7.52 (2H, dd, J = 5.04; 8.27, ArH). 13C NMR
(125 MHz, CDCl3), d, ppm: 9.4 (CH2); 22.4 (7xCH2); 22.8
(CH2); 23.8 (7xCH); 23.9 (7xCH3); 25.7 (7xCH3); 34.0
(CH2); 36.0 (CH2); 41.6 (CH); 42.4 (CH2); 43.8 (CH); 45.2
(CH); 46.4 (CH); 51.5 (CH); 54.9 (CH); 83.7 (CH); 124.4
(Cq); 127.1 (Cq); 127.8 (CAr); 128.2 (CAr); 128.3 (CAr);
128.7 (CAr); 128.9 (CAr); 129.0 (2xCAr); 132.0 (CAr); 132.1
(CAr); 135.7 (Cq); 155.6 (Cq); 167.2 (C ¼ O); 176.0 (C ¼ O);
176.3 (C ¼ O). HRMS: - Found, m/z: 1364.5099 [Mþ þ H].
C56H90N3O16Si8Br Calculated, m/z: 1363.3659 [M]þ.
[[C46H88N2O15Si8] þ 2K] þ 2. C46H88N2O15Si8 Calculated,
m/z: 1133,8946 [Mþ].
General procedure for 1,3-dipolar cycloaddition
reaction of POSS derivatives (5a–c, 6 and 7)
To a solution of carboximidoyl chloride (1 mmol or 3 mmol
for Trisnorbornenylisobutyl POSS) in diethyl ether was
added
Trisnorbornenylisobutyl POSS) (1 mmol), and the mixture
was cooled to 0 ꢁC. Then, trimethylamine (2 mmol) was
added dropwise and the mixture was stirred overnight (0 ꢁC
to r.t.). The organic phase was evaporated to dryness and
the crude residue purified by combiflash chromatography.
(4a-c,
Norbornenylethylisobutyl
POSS
or
N-[3-(isobutylpolihedral oligomeric
silsesquioxanyl)propyl]-2-(4,8-Methano-3-(4-
bromophenyl)-4,4a,8,ekzo-8a-tetrahydro-ekzo-3aH-
isoxazol[5,4-f]isoindol-5,7(6H,7aH)-endo-dion-6-yl)-3-
methyl pentanamide (5c)
N-[3-(isobutylpolihedral oligomeric
silsesquioxanyl)propyl]-2-(4,8-Methano-3-(4-
bromophenyl)-4,4a,8,ekzo-8a-tetrahydro-ekzo-3aH-
isoxazol[5,4-f]isoindol-5,7(6H,7aH)-endo-dion-6-yl)
propanamide (5a)
White Solid; mp 95–97 ꢁC; Yield: 84%. IR: ꢀ cmꢀ1 2953
(Aliphatic C–H), 1702 (C ¼ O), 1591 (Si–O–Si), 1089
(Si–O–R), 1463, 1399, 1382, 836. 1H NMR (500 MHz,
CDCl3), d, ppm (J, Hz): 0.53 (16H, dd, J ¼ 2.52; 6.93,
CH2–Si); 0.80 (3H, q, J ¼ 7.56, CH3); 0.88 (42H, d, J ¼ 6.62,
CH3); 0.95 (3H, t, J ¼ 6.62, CH3); 0.98–1.08 (2H, m, CH2);
White solid. mp 102–105 ꢁC; Yield 75%. IR ꢀ cmꢀ1 2953
and 2870 (Aliphatic C–H), 1726 and 1701 (C ¼ O), 1591
1
(Si–O–Si), 1493, 1399, 1382, 1086 (Si–O–R), 744. H NMR
(500 MHz, CDCl3), d, ppm (J, Hz): 0.59 (14H, dd, J = 3.46;
7.25, 7xCH2-Si); 0.82-0.90 (2H, m, CH2); 0.94 (42H, d,
J = 6.62, 14xCH3); 0.98 (3H, d, J = 6.62, CH3); 1.20–1.30 (3H,
m, H10a, H10s, CH); 1.55 (1H, d, J = 11.35, CH); 1.63 (2H, t,
J ¼ 7.56, CH2); 1.81–1.92 (7H, m, 7xCH); 2.94 (1H, t,
J = 5.99, H1); 3.14–3.33 (5H, m, N–CH2, H9n, H8n, H7); 4.72
(1H, q, J ¼ 7.25; 14.50, CH); 5.72 (1H, dt, J ¼ 5.67; 28.37,
NH); 7.52 (2H, d, J ¼ 2.52, ArH); 7.53 (2H, d, J ¼ 1.89,
ArH). 13C NMR (125 MHz, CDCl3), d, ppm: 9.4 (CH2); 14.4
(CH3); 14.7 (CH); 22.5 (7xCH2); 22.8 (CH2); 23.8 (7xCH3);
23.9 (7xCH3); 25.6 (7xCH); 36.3 (CH2); 41.9 (CH); 42.4
(CH2); 43.9 (CH); 44.4 (CH); 45.7 (CH); 46.4 (CH); 83.8
(CH); 124.3 (Cq); 127.5 (Cq); 128.3 (CAr); 128.4 (CAr);
132.0 (2xCAr); 155.6 (Cq); 167.7 (C ¼ O); 175.8 (C ¼ O);
176.3 (C ¼ O). HRMS: - Found, m/z: 1288.3026 [Mþ þ H],
1310.4561 [Mþ þ Na]. C50H86N3O16Si8Br Calculated, m/z:
1287.3346 [M]þ.
1.22–1.32 (1H, m, CH2); 1.50–1.55 (3H, m, H10a, H10s
,
CH2); 1.77 (7H, hept, CH); 2.48–2.54 (1H, m, CH); 2.91
(1H, brd, J ¼ 5.04, H1); 3.01–3.07 (1H, m, N–CH2); 3.10
(1H, s, H7); 3.16–3.20 (2H, m, H2, H6); 3.24–3.30 (1H, m,
N–CH2); 3.47 (1H, d, J ¼ 8.51, H9n); 4.28 (1H, d, J ¼ 11.35,
CH); 4.56 (1H, dt, J ¼ 8.31; 11.04, H8n), 6.54 (1H, s, NH);
7.44–7.48 (4H, m, ArH). 13C NMR (125 MHz, CDCl3), d,
ppm: 9.5 (CH2); 10.2 (CH3); 16.1 (CH3); 22.5 (CH2); 22.9
(7xCH2); 23.1 (CH2); 23.9 (7xCH); 25.7 (14xCH3); 31.8
(CH); 32.1 (CH); 36.2 (CH2); 42.1 (CH2); 43.8 (CH); 45.9
(CH); 46.4 (CH); 52.4 (CH); 62.4 (CH); 83.4 (CH); 124.7
(Cq); 127.1 (Cq); 128.3 (2xCAr); 132.2 (2xCAr); 155.5
(Cq); 168.0 (C ¼ O); 176.8 (C ¼ O); 177.0 (C ¼ O). HRMS:
- Found, m/z: (z ¼ 2): 679.6650 [(C53H92N3O16Si8Br)þ
2Na] þ 2(–H2O), 687.6582 [(C53H92N3O16Si8Br)þ2Na] þ 2.
C53H92N3O16Si8Br Calculated, m/z: 1331.8946 [Mþ].
N-[3-(isobutylpolihedral oligomeric
6 -(4-Bromophenyl)-2a,3,3a,6a,7,7a-hexahydro-3,7-
methano-1-[3-(isobutylpolihedral oligomeric
silsesquioxanyl)propyl] [3,4-f]benzisoxazole (6a)
silsesquioxanyl)propyl]-2-(4,8-Methano-3-(4-
bromophenyl)-4,4a,8,ekzo-8a-tetrahydro-ekzo-3aH-
isoxazol[5,4-f]isoindol-5,7(6H,7aH)-endo-dion-6-yl)-3-
phenyl propanamide (5b)
White solid. Yield: 35%. IR: ꢀ cmꢀ1 2953, 2925, 2907, 2858
White solid; mp 131–133.5 ꢁC; Yield: 65%. IR ꢀ cmꢀ1 3307 (Aliphatic CH), 1590 (S–O–Si), 1464, 1382, 1365, 1087
1
(N–H), 2953 and 2869 (Aliphatic C–H), 1705 (C ¼ O), 1541 (Si–O–R). H NMR (500 MHz, CDCl3), d, ppm (J, Hz): 0.60
(Si–O–Si), 1463, 1399, 1228, 1086 (Si-O-R), 836, 740. 1H (16 H, dt, J ¼ 1.89; 6.93, CH2–Si); 0.95 (21H, t, J ¼ 1.89,
NMR (500 MHz, CDCl3), d, ppm (J, Hz): 0.55-0.59 (2 H, m, CH3); 0.96 (21H, t, J ¼ 1.89, CH3); 1.36–1.55 (6H, m, CH2);

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
265
1.84 (7H, hept, J ¼ 4.09, CH); 2.22 (1H, brs, CH); 2.39 (1H, 49.5 (3xCH2); 58.4 (CH); 84.2 (CH); 127.1 (2x ¼ CH); 127.4
brs CH); 2.55 (1H, brd, J ¼ 3.78, CH); 3.70 (1H, d, J ¼ 8.19, (=CH); 127.6 (=CH); 132.3 (CAr); 132.4 (Cq); 136.9
CH); 4.56 (1H, d, J ¼ 8.19, CH); 7.51 (2H, d, J ¼ 8.82, HAr); (2xCAr); 152.9 (Cq). HRMS: - Found, m/z: 1434.4000
7.54 (2H, d, J ¼ 8.82, HAr). 13C NMR (125 MHz, CDCl3), d, [Mþ þ H].
C66H123NO12SSi8.
Calculated,
m/z:
1433.6459 [Mþ].
ppm: 11.1 (CH2); 22.5 (7xCH2); 23.8 (7xCH3); 24.0 (7xCH3);
25.3 (CH2); 25.7 (7xCH); 33.7 (CH2); 34.6 (CH2); 39.3 (CH);
40.1 (CH); 46.0 (CH); 57.1 (CH); 84.4 (CH); 123.9 (Cq);
128.2 (2xCar); 128.4 (Cq); 131.9 (2xCar); 156.2 (Cq). HRMS:
4 -(4-Bromophenyl)-2a,3,3a,6a,7,7a-hexahydro-3,7-
methano-1-[3-(isobutylpolihedral oligomeric
silsesquioxanyl)propyl] [3,4-f]benzisoxazoyl
dinorbornenylisobutyl POSS (7b)
-
Found, m/z: 1134.1570 [Mþ þ H]. C44H80BrNO13Si8.
Calculated, m/z: 1133.2697 [Mþ].
Colorless oil. Yield: 35%. IR: ꢀ cmꢀ1 3057 (Aromatic CH),
2952, 2908 and 2867 (Aliphatic CH), 1579 (Si–O–Si), 1464,
1449, 1401, 1076, 1048 (Si–O–R). 1H NMR (500 MHz,
CDCl3), d, ppm (J, Hz): 0.09 (14H, brs, CH2–Si); 0.14 (6H,
d, J ¼ 3.15, CH2–Si); 0.45–0.48 (2H, m, CH2); 0.52–0.56
(18H, m, CH3–Si); 0.96 (42H, d, J ¼ 6.62, CH3); 1.03–1.11
(4H, m, CH2); 1.21 (2H, d, J ¼ 7.88, CH2); 1.26 (2H, d,
J ¼ 10.4, Ha); 1.29–1.39 (7H, m, 1Ha, 2Hs, 2CH2) 1.57 (1H,
d, J ¼ 11.35, Hs); 1.78–1.85 (7H, m, CH); 1.90–1.96 (3H, m,
CH); 2.54 (1H, brd, J ¼ 4.41, H bridge); 2.62 (1H, brd,
J ¼ 3.46, H bridge); 2.73 (2H, brs, H bridge); 2.78 (2H, brs,
H bridge); 3.41 (1H, d, J ¼ 8.19, CH); 4.85 (1H, d, J ¼ 8.19,
CH–O); 5.89 (2H, dd, J ¼ 2.83; 5.67, =CH); 6.09 (2H, dd,
J ¼ 2.83; 5.67, =CH); 7.05 (1H, dd, J ¼ 3.46; 5.04, Har); 7.25
(1H, dd, J ¼ 1.26; 3.46, Har); 7.35 (1H, dd, J ¼ 1.26; 5.04,
Har). 13C NMR (125 MHz, CDCl3), d, ppm: 0.23 (2xCH3);
0.30 (2xCH3); 0.39 (2xCH3); 17.0 (3xCH2); 22.4 (CH2); 23.7
(3xCH2); 23.8 (CH); 23.9 (2xCH); 24.0 (2xCH); 25.0
(2xCH2); 25.1 (CH2); 25.6 (CH); 25.8 (7xCH3); 26.0
(7xCH3); 27.9 (CH2); 32.3 (3xCH2); 33.8 (CH); 34.6 (CH2);
39.9 (3xCH); 42.2 (3xCH); 42.5 (CH); 45.0 (3xCH); 49.5
(3xCH2); 58.4 (CH); 84.2 (CH); 127.1 (=CH); 127.4 (=CH);
127.6 (=CH); 132.3 (CAr); 132.4 (Cq); 136.9 (2xCAr); 152.9
4 -(4-Bromophenyl)-2a,3,3a,6a,7,7a-hexahydro-3,7-
methano-1-[3-(isobutylpolihedral oligomeric
silsesquioxanyl)propyl] [3,4-f]benzisoxazole (6b)
White solid. m.p.: 109-111 ꢁC. Yield: 40%. IR: ꢀ cmꢀ1 2953,
2926, 2869 (Aliphatic CH), 1590 (Si–O-Si), 1464, 1382,
1
1365, 1087 (Si-O-R). H NMR (500 MHz, CDCl3), d, ppm
(J, Hz): 0.60 (16H, dt, J ¼ 2.20; 6.93, CH2-Si); 0.95 (21H, t,
J ¼ 2.20, CH3); 0.97 (21H, t, J ¼ 2.20, CH3); 1.23 (1H, d,
J ¼ 10.4, CH2); 1.40–1.45 (4H, m, CH2); 1.52 (1H, d,
J ¼ 10.4, CH2); 1.86 (8H, hept, J ¼ 6.62, CH); 2.42 (1H, brs,
CH); 2.63 (1H, brs CH); 3.38 (1H, d, J ¼ 8.19, CH); 4.86
(1H, d, J ¼ 8.19, CH); 7.52 (2H, d, J ¼ 8.82, HAr); 7.57 (2H,
d, J ¼ 8.82, HAr). 13C NMR (125 MHz, CDCl3), d, ppm: 11.0
(CH2); 22.4 (7xCH2); 23.8 (7xCH3); 23.9 (7xCH3); 25.4
(CH2); 25.7 (7xCH); 33.6 (CH2); 34.7 (CH2); 39.2 (CH); 40.1
(CH); 45.8 (CH); 57.0 (CH); 84.2 (CH); 123.8 (Cq); 128.2
(2xCar); 128.3 (Cq); 131.9 (2xCar); 156.1 (Cq). HRMS: -
Found, m/z: 1134.1000 [Mþ þ H]. C44H80BrNO13Si8.
Calculated, m/z: 1133.2697 [Mþ].
6 -(4-Bromophenyl)-2a,3,3a,6a,7,7a-hexahydro-3,7-
methano-1-[3-(isobutylpolihedral oligomeric
silsesquioxanyl)propyl] [3,4-f]benzisoxazoyl
dinorbornenylisobutyl POSS (7a)
(Cq). HRMS:
-
Found, m/z: 1434.3450 [Mþ þ H].
C66H123NO12SSi8. Calculated, m/z: 1433.6459 [Mþ].
Colorless oil. Yield: 32%. IR: ꢀ cmꢀ1 3058 (Aromatic CH),
2952, 2933, 2909 and 2867 (Aliphatic CH), 1580 (Si–O–Si),
1464, 1401, 1331, 1076 and 1047 (Si–O–R). 1H NMR
(500 MHz, CDCl3), d, ppm (J, Hz): 0.09 (14H, brs, CH2-Si);
0.13 (6H, dd, J ¼ 1.89; 6.62, CH2–Si); 0.18 (6H, s, CH3–Si);
0.44–0.48 (2H, m, CH2); 0.52–0.56 (12H, m, CH3–Si); 0.96
(42H, d, J ¼ 6.62 Hz, CH3); 1.03–1.11 (4H, m, CH2); 1.19
(2H, d, J ¼ 7.88, CH2); 1.25–1.29 (5H, m, Ha, Hs, CH2); 1.38
(4H, dd, J ¼ 1.89; 7.88, Ha, Hs, CH2); 1.57 (1H, d, J ¼ 1.26;
11.98 Hz, Hs); 1.78-1.86 (7H, m, CH); 1.90–1.96 (3H, m,
CH), 2.54 (2H, brs, H bridge); 2.73 (2H, brs, H bridge); 2.77
(2H, brs, H bridge); 3.67 (1H, d, J ¼ 8.51, CH); 4.55 (1 H, d,
J ¼ 8.19, CH–O); 5.88 (2H, dd, J ¼ 2.83; 5.67, =CH); 6.09
(2H, dd, J ¼ 3.15; 5.67, =CH); 7.05 (1H, dd, J ¼ 3.78; 5.04,
Har); 7.22 (1H, dd, J ¼ 0.94; 3.78, Har); 7.36 (1H, dd,
J ¼ 0.94; 5.04, Har). 13C NMR (125 MHz, CDCl3), d, ppm:
0.23 (2xCH3); 0.30 (2xCH3); 0.39 (2xCH3); 17.0 (3xCH2);
22.4 (CH2); 23.7 (3xCH2); 23.8 (CH); 23.9 (2xCH); 24.0
Preparation of POSS-based fused Spiro-1,3-
indandionolylpyrrolidine Compounds 8 and 9
A sealed tube containing ninhydrine (1 mmol, 3 mmol
for 9), sarcosine (1 mmol, 3 mmol for 9) and
NorbornenylethylIsobutyl POSS or TrisnorbornenylIsobutyl
POSS (1 mmol) in EtOH/dioxane (1:1, 20 mL) was heated at
65 ꢁC for 24 h under nitrogen atmosphere.
After completion of the reaction with TLC control, the
solvent was evaporated under reduced pressure, and the
residue purified by combiflash chromatography.
Spiro-1,3-indandionolylpyrrolidine-fused
norbornenylethyl isobutyl POSS (8)
Yellow solid. m.p.: 126–129 ꢁC Yield: 52%. IR: ꢀ cmꢀ1 2952,
2926, 2908 and 2868 (Aliphatic CH), 1742 and 1705
(C ¼ O), 1598 (Si–O–Si), 1463, 1085 (Si–O–R). 1H NMR
(2xCH); 25.0 (2xCH2); 25.1 (CH2); 25.6 (CH); 25.8 (7xCH3); (500 MHz, CDCl3), d, ppm (J, Hz): 0.14 (1H, hept, J ¼ 5.67,
26.0 (7xCH3); 27.9 (CH2); 32.3 (3xCH2); 33.8 (CH); 34.6 CH2–Si); 0.29 (1H, hept, J ¼ 5.67, CH2–Si); 0.53 (6H, d,
(CH2); 39.9 (3xCH); 42.2 (3xCH); 42.5 (CH); 45.0 (3xCH); J ¼ 6.93, CH2-Si); 0.57 (8H, d, J ¼ 6.93, CH2–Si); 0.82–0.85

266
E. B. ERSOY ET AL.
(1H, m, CH2); 0.88 (17H, d, J ¼ 6.62, CH3); 0.94 (25H, d,
J ¼ 6.62, CH3); 0.97–0.99 (1H, m, CH2); 1.06–1.13 (1H, m,
CH2); 1.18 (1H, d, J ¼ 9.77, Ha); 1.24–1.27 (1H, m, Hs);
1.30–1.36 (1H, m, CH2); 1.76 (4H, hept, J ¼ 6.93, CH);
1.82–1.87 (4H, m, CH); 2.13 (1H, brd, J ¼ 4.09, CH);
2.24–2.27 (2H, m, CH2); 2.28 (3H, s, CH3); 2.34 (1H, brs,
CH); 2.95 (1H, dd, J ¼ 2.83; 9.77, CH); 3.46-3.49 (1H, m,
CH); 7.82-7.85 (2H, m, Har); 7.92 (1H, dd, J ¼ 3.15; 6.62,
Har), 7.96 (1H, dd, J ¼ 3.15; 6.62, Har). 13C NMR
(125 MHz, CDCl3), d, ppm: 10.6 (CH2); 22.4 (4xCH2); 22.5
(3xCH2); 23.8 (14xCH3); 24.7 (CH2); 25.7 (8xCH); 35.6
(CH2); 36.0 (CH2); 41.9 (2xCH); 42.1 (CH); 48.6 (CH); 50.5
(CH3); 61.4 (CH2); 122.9 (Car); 123.0 (Car); 135.8 (2xCar);
139.8 (Cq); 141.9 (2xCq); 195.0 (2xC ¼ O). HRMS: - Found,
m/z: 1124.4000 [Mþ þ H]. C48H85NO14Si8. Calculated, m/z:
1123.4124 [M]þ.
References
[1] Scott, D. W. Thermal Rearrangement of Branched-Chain
Methylpolysiloxanes. J. Am. Chem. Soc. 1946, 68, 356–358.
DOI: 10.1021/ja01207a003.
[2] Jianjun, D.; Joseph, T. P.; John, R. H.; Catherine, E. F.-C.;
Brent, D. V.; Alan, R. E. Polyhedral Oligomeric Silsesquioxanes:
A New Class of Amphiphiles at the Air/Water Interface. J. Am.
Chem. Soc. 2002, 124, 15194–15195. DOI: 10.1021/ja027860v.
[3] Cordes, D. B.; Paul D. Lickiss, P. D.; Rataboul, F. Recent
Developments in the Chemistry of Cubic Polyhedral
Oligosilsesquioxanes. Chem. Rev. 2010, 110, 2081–2173. DOI:
10.1021/cr900201r.
[4] Wu, J.; Mather, P. T. POSS Polymers: Physical Properties and
Biomaterials Applications. Polym. Rev. 2009, 49, 25–63. DOI:
10.1080/15583720802656237.
[5] Hurd, C. B. Studies on Siloxanes. I. The Specific Volume and
Viscosity in Relation to Temperature and Constitution. J. Am.
Chem. Soc. 1946, 68, 364–370. DOI: 10.1021/ja01207a005.
[6] Hui, Z.; Qun, Y.; Jianwei, X. Polyhedral Oligomeric
Silsesquioxane-based Hybrid Materials and Their Applications.
Mater. Chem. Front. 2017, 1, 212–230. DOI: 10.1039/
c6qm00062b.
[7] Daisuke, I.; Yuh, S.; Kazuki, N.; Tsukasa, N.; Hisashi, F. Self-
Organization of Silsesquioxane-Modified Gold Nanoparticles
and Immobilization of Their Polythiophene Nanocomposite
Films onto Electrode Surface. Phosphorus, Sulfur Silicon Relat.
Elem. 2010, 185, 1206–1213. DOI: 10.1080/10426501003773597.
[8] Zhenghui, L.; Dingcai, W.; Yeru, L.; Ruowen, F.; Krzysztof, M.
Synthesis of Well-Defined Microporous Carbons by Molecular-
Scale Templating with Polyhedral Oligomeric Silsesquioxane
Moieties. J. Am. Chem. Soc. 2014, 136, 4805–4808. DOI:
10.1021/ja412192v.
[9] Yongjun, G.; Atsuko, E.; Kazuaki, K.; Yuan, C. L. Efficient
Preparation of Glycoclusters from Silsesquioxanes. Org. Lett.
2004, 6, 3457–3460. DOI: 10.1021/ol040043a.
[10] Tanaka, K.; Chujo, Y. Advanced Functional Materials Based on
Polyhedral Oligomeric Silsesquioxane (POSS). J. Mater. Chem.
2012, 22, 1733–1746. DOI: 10.1039/C1JM14231C.
Spiro-1,3-indandionolylpyrrolidine-fused norbornenyl
dinorbornenylisobutyl POSS (9)
Yellow oil. Yield: 57%. IR: ꢀ cmꢀ1 3057 (Aromatic CH),
2952, 2908 and 2867 (Aliphatic CH), 1743 and 1707
(C ¼ O), 1598 (Si–O–Si), 1464, 1450, 1401, 1077, 1050
(Si–O–R). 1H NMR (500 MHz, CDCl3), d, ppm (J, Hz):
0.03–0.10 (16H, m, CH2–Si); 0.44–0.49 (4H, m, CH2–Si);
0.51–0.55 (18H, m, CH2–Si); 0.87–0.91 (4H, m, CH2);
0.92–0.96 (42H, m, CH3); 1.02–1.07 (3H, m, CH2);
1.17–1.21 (3H, m, CH2); 1.24–1.27 (3H, m, Ha); 1.36–1.39
(3H, m, Hs and CH2); 1.66–1.72 (2H, m, Hs and CH2);
1.78–1.85 (8H, m, CH); 1.89–1.94 (2H, m, CH); 2.12 (1H,
brs, H1); 2.23 (1H, brs, H7); 2.25 (2H, d, J ¼ 5.04, CH2); 2.28
(3H, d, J ¼ 5.35, N–CH3); 2.72 (2H, brs, H1); 2.77 (2H, brs,
H7); 2.96 (1H, dd, J ¼ 3.46; 9.14, CH); 3.46–3.50 (1H, m,
CH–O); 5.88 (2H, dd, J ¼ 2.83; 5.35, =CH); 6.07-6.09 (2H,
m, =CH); 7.82–7.85 (2H, m, Har); 7.91–7.93 (1H, m, Har);
7.95–7.97 (1H, m, Har). 13C NMR (125 MHz, CDCl3), d,
ppm: 0.2 (CH3); 17.0 (2xCH2); 22.4 (CH2); 23.7 (2xCH2);
23.8 (CH3); 23.9 (2xCH3); 24.0 (2xCH3); 25.0 (3xCH2); 25.6
(2xCH3); 25.8 (7xCH3); 26.0 (5xCH3); 27.9 (2xCH2); 32.3
(4xCH2); 35.7 (CH2); 36.1 (CH2); 39.7 (2xCH); 39.9 (3xCH);
40.5 (2xCH); 42.1 (3xCH); 42.5 (4xCH); 42.9 (4xCH); 44.9
(2xCH); 48.6 (2xCH); 49.5 (3xCH2); 57.9 (CH3); 61.4 (CH2);
122.9 (Car); 132.3 (Cq); 135.9 (Car); 136.8 (Car); 136.9
(Car); 141.9 (Cq); 142.0 (Cq); 207.3 (2xC ¼ O). HRMS: -
Found, m/z: 1496.5200 [Mþ þ H]. C72H129NO13Si10.
Calculated, m/z: 1495.7157 [Mþ].
[11] Kuo, S.-W.; Chang, F.-C. POSS Related Polymer
Nanocomposites. Prog. Polym. Sci. 2011, 36, 1649–1696. DOI:
10.1016/j.progpolymsci.2011.05.002.
[12] Liu, Y. R.; Huang, Y. D.; Liu, L. Thermal Stability of POSS/
methylsilicone Nanocomposites. Compos. Sci. Technol. 2007, 67,
2864–2876. DOI: 10.1016/j.compscitech.2007.01.023.
[13] Lewicki, J. P.; Patel, M.; Morrell, P.; Liggat, J.; Murphy, J.;
Pethrick, R. The Stability of Polysiloxanes Incorporating Nano-
scale Physical Property Modifiers. Sci. Technol. Adv. Mater.
2008, 9, 024403. DOI: 10.1088/1468-6996/9/2/024403.
[14] Zhang, H. X.; Lee, H. Y.; Shin, Y. J.; Lee, D. H.; Noh, S. K.
Effect of 3rd Monomer Addition on Styrene/styryl-polyhedral
Oligomeric
Silsesquioxane
(POSS)
Copolymerization.
Macromol. Res. 2009, 17, 352–355. DOI: 10.1007/BF03218874.
[15] Kwon, Y.; Kim, K. H. Synthesis of Norbornene Block
Copolymers Containing Polyhedral Oligomeric Silsesquioxane
by Sequential Ring-opening Metathesis Polymerization.
Macromol. Res. 2006, 14, 424–429. DOI: 10.1007/BF03219105.
[16] Feng, Y.; Jia, Y.; Guang, S. Y.; Xu, H. Y. Study on Thermal
Enhancement Mechanism of POSS-containing Hybrid
Nanocomposites and Relationship between Thermal Properties
and Their Molecular Structure. J. Appl. Polym. Sci. 2010, 115,
2212–2220. DOI: 10.1002/app.31319.
[17] Feng, Y.; Jia, Y.; Xu, H. Y. Preparation and Thermal Properties
of Hybrid Nanocomposites of Poly(methyl Methacrylate)/
Octavinyl Polyhedral Oligomeric Silsesquioxane Blends. J. Appl.
Polym. Sci. 2009, 111, 2684–2690. DOI: 10.1002/app.29240.
[18] Ma, X.-M.; Wang, B.; Zhang, M.-X.; Min, F.-F.; He, J. Synthesis
and Thermal Characterizations of Pmma Nanocomposite
Functionalized by Polyhedral Oligomeric Silsesquioxane.
Funding
The authors express their grateful thanks to Yildiz Technical University
Scientific Research Projects Coordination Department for financial sup-
port of this work (2015-01-02-GEP03).
ORCID
Elif Basak Ersoy
Omer Tahir Gunkara
http://orcid.org/0000-0003-3528-5045
http://orcid.org/0000-0003-3528-5045

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
267
Phosphorus, Sulfur Silicon Relat. Elem. 2013, 188, 1819–1826. [36] Karthikeyan, K.; Sivakumar, P. M.; Doble, M.; Perumal, P. T.
DOI: 10.1080/10426507.2013.788001.
Synthesis, antibacterial Activity Evaluation and QSAR Studies
of Novel Dispiropyrrolidines. Eur. J. Med. Chem. 2010, 45,
3446. DOI: 10.1016/j.ejmech.2010.04.035.
[19] Zhang, W.; Muller, A. H. E. Architecture, self-assembly and
Properties of Well-defined Hybrid Polymers Based on
Polyhedral Oligomeric Silsequioxane (POSS). Prog. Polym. Sci.
2013, 38, 1121–1162. DOI: 10.1016/j.progpolymsci.2013.03.002.
[20] Zhang, Q.; He, H.; Xi, K.; Huang, X.; Yu, X.; Jia, X. Synthesis
of N-Phenylaminomethyl POSS and Its Utilization in
Polyurethane. Macromolecules 2011, 44, 550–557. DOI: 10.1021/
ma101825j.
[21] Chen, P.; Huang, X.; Zhang, Q.; Xi, K.; Jia, X. Hybrid Networks
Based on Poly (styrene-co-maleic Anhydride) and N-phenyla-
minomethyl POSS. Polymer 2013, 54, 1091–1097. DOI: 10.1016/
j.polymer.2012.12.047.
[37] Purushothaman, S.; Prasanna, R.; Niranjana, P.; Raghunathan,
R.; Nagaraj, S.; Rengusamy, R. Synthesis, antimicrobial and
Antioxidant Evaluation of Quinolines and Bis(indolyl)
Methanes. Bioorg. Med. Chem. Lett. 2010, 20, 7291. DOI:
10.1016/j.bmcl.2010.10.075.
[38] Kumar, R. R.; Perumal, S.; Senthilkumar, P.; Yogeeswari, P.;
Sriram, D. Discovery of Antimycobacterial Spiro-piperidin-4-
ones: An Atom Economic, Stereoselective Synthesis, and
Biological Intervention. J. Med. Chem. 2008, 51, 5731. DOI:
10.1021/jm800545k.
[39] Galliford, C. V.; Scheidt, K. A. Pyrrolidinyl-Spirooxindole
Natural Products as Inspirations for the Development of
Potential Therapeutic Agents. Angew. Chem. Int. Ed. 2007, 46,
8748. DOI: 10.1002/anie.200701342.
[40] Rosenberg, S.; Leino, R. Synthesis of Spirocyclic Ethers.
Synthesis 2009, 16, 2651. DOI: 10.1055/s-0029-1216892.
[41] Padwa, A.; Bur, S. K. The Domino Way to Heterocycles.
Tetrahedron 2007, 63, 5341. DOI: 10.1016/j.tet.2007.03.158.
[42] Francke, W.; Kitching, W. Spiroacetals in Insects. Curr. Org.
Chem. 2001, 5, 233. DOI: 10.2174/1385272013375652.
[43] Antonchick, A. P.; Gerding-Reimers, C.; Catarinella, M.;
Schu€rmann, M.; Preut, H.; Ziegler, S.; Rauh, d.; Waldmann, H.
Highly Enantioselective Synthesis and Cellular Evaluation of
Spirooxindoles Inspired by Natural Products. Nature Chem.
2010, 2, 735. DOI: 10.1038/nchem.730.
[44] Yamamoto, Y.; Yamamoto, S.; Yatagai, H.; Ishihara, Y.;
Maruyama, K. Lewis Acid Mediated Reactions of Organocopper
Reagents. Entrainment in the Conjugate Addition to
a,b-Unsaturated Ketones, esters, and Acids via the RCuꢂBF3
System. J. Org. Chem. 1982, 47, 119–126. DOI: 10.1021/
jo00340a02.
[45] Frady, G. A.; Michael, G. G.; Ashraf, G. Design and Synthesis
of Novel Chiral Dirhodium(II) Carboxylate Complexes for
Asymmetric Cyclopropanation Reactions. Chem. Eur. J. 2016,
22, 3447–3461. DOI:10.1002/chem.201504817.
[46] Fatma, A.; Omer, T. G.; Elif, B. E.; Nuket, O.; Dieter, E. K.
Synthesis of New N-norbornylimide Substituted Amide
Derivatives, their Reductive Heck and Domino Heck Reactions.
Arkivoc 2017, 5, 244–256. DOI: 10.24820/ark.5550190.p010.304.
[47] Laura, S.; Ulrich, G.; Bernd, C. Synthesis and Characterization
of Para-Substituted N,N’-Dihydroxybenzamidines and Their
Derivatives as Model Compounds for a Class of Prodrugs. Eur.
J. Org. Chem. 2014, 9, 1961–1975.
[22] Milliman, H. W.; Boris, D.; Schiraldi, D. A. Experimental
Determination of Hansen Solubility Parameters for Select POSS
and Polymer Compounds as
a Guide to POSS–Polymer
Interaction Potentials. Macromolecules 2012, 45, 1931–1936.
DOI: 10.1021/ma202685j.
[23] Raftopoulos, K. N.; Koutsoumpis, S.; Jancia, M.; Lewicki, J. P.;
Kyriakos, K.; Mason, H. E.; Harley, S. J.; Hebda, E.; Papadakis,
C. M.; Pielichowski, K.; Pissis, P. Reduced Phase Separation and
Slowing of Dynamics in Polyurethanes with Three-Dimensional
POSS-Based Cross-Linking Moieties. Macromolecules 2015, 48,
1429–1441. DOI: 10.1021/ma5023132.
[24] Jiang, S. D.; Tang, G.; Bai, Z. M.; Wang, Y. Y.; Hu, Y.; Song, L.
Surface Functionalization of MoS2 with POSS for Enhancing
Thermal, flame-retardant and Mechanical Properties in PVA
Composites. RSC Adv. 2014, 4, 3253–3262. DOI: 10.1039/
C3RA45911J.
[25] Chua, M. L.; Shao, L.; Low, B. T.; Xiao, Y.; Chung, T. S.; Chua,
M. L.; Shao, L.; Low, B. T.; Xiao, Y.; Chung, T. S.
Polyetheramine–polyhedral
Oligomeric
Silsesquioxane
Organic–inorganic Hybrid Membranes for CO2/H2 and CO2/N2
Separation. J. Membr. Sci. 2011, 385, 40–48. DOI: 10.1016/
j.memsci.2011.09.008.
[26] Le, N. L.; Wang, Y.; Chung, T. S. Pebax/POSS Mixed Matrix
Membranes for Ethanol Recovery from Aqueous Solutions via
Pervaporation. J. Membr. Sci. 2011, 379, 174–183. DOI:
10.1016/j.memsci.2011.05.060.
[27] Sambhy, V.; MacBride, M. M.; Peterson, B. R.; Sen, A. Silver
Bromide Nanoparticle/Polymer Composites: Dual Action
Tunable Antimicrobial Materials. J. Am. Chem. Soc. 2006, 128,
9798–9808. DOI: 10.1021/ja061442z.
ꢀ
~
ꢀ
ꢀ
[28] Alvarez-Paino, M.; Munoz-Bonilla, A.; Fernandez-Garcıa, M.
Antimicrobial Polymers in the Nano-World. Nanomaterials
2017, 7, 48. DOI: 10.3390/nano7020048.
[29] Callow, J. A.; Callow, M. E. Trends in the Development of
Environmentally Friendly Fouling-resistant Marine Coatings.
Nat. Commun. 2011, 2, 244–253. DOI: 10.1038/ncomms1251.
[30] Jiao, Y.; Niu, L.; Ma, S.; Li, J.; Tay, F. R.; Chen, J. Quaternary
Ammonium-based Biomedical Materials: State-of-the-art, toxi-
cological Aspects and Antimicrobial Resistance. Prog. Polym.
Sci. 2017, 71, 53–90. DOI: 10.1016/j.progpolymsci.2017.03.001
[31] Simoncic, B.; Tomsic, B. Structures of Novel Antimicrobial
[48] Jiang, K.-M.; Jin, Y.; Lin, J. 1. 3-Dipolar Cycloaddition of Uracil
Derivatives with Nitrile Oxides: Synthesis of [1,2,4]oxadia-
zolo[4,5-c]pyrimidine-5,7(6H)-Dione Derivatives. Tetrahedron
2017, 73, 6662–6668. DOI: 10.1016/j.tet.2017.10.024.
[49] Darvatkar, N. B.; Wankhede, K. S.; Bhilare, S. V.; Deorukhkar,
A. R.; Raut, D. G.; Vaidya, V. V.; Trivedi, G. K.; Salunkhe,
M. M. 1,3-Dipolar Cycloaddition of Nitrile Oxides with
Symmetrical Tri- and Polycyclic Strained Olefins. J. Heterocyclic
Chem. 2010, 47, 1004. DOI: 10.1002/jhet.421.
Agents for Textiles
- A Review. Text. Res. J. 2010, 80,
1721–1737. DOI: 10.1177/0040517510363193.
[50] Singh, G.; Elango, M.; Subramanian, V.; Ishar, M. P. S. Regio-
and Exo-p-Facial Selective 1,3-Dipolar Cycloaddition of a-(3-
Pyridyl)-N-phenylnitrone to Norbornadiene: Activation of a
p-Bond of Norbornadiene and Control of Regiochemistry of
Nitrone Cycloaddition by Nitrone Addition to the Other
Double Bond. Heterocycles 2006, 68, 1409–1419. DOI: 10.3987/
COM-06-10732.
[51] Chapyshev, S. V.; Anisimov, V. M. Stereo- and Regioselective
Cycloaddition of Norbornene to 2,4,9-Triazidopyridine. Chem.
Heterocycl. Compd. 1997, 33, 1315–1324. DOI: 10.1007/
BF02320334.
[32] Ren, W.; Cheng, W.; Wang, G.; Liu, Y. Developments in
Antimicrobial Polymers. J. Polym. Sci. Part A: Polym. Chem.
2017, 55, 632–639. DOI: 10.1002/pola.28446.
[33] Huang, K.-S.; Yang, C.-H.; Huang, S.-L.; Chen, C.-Y.; Lu, Y.-Y.;
Lin, Y.-S. Recent Advances in Antimicrobial Polymers: A Mini-
Review. IJMS. 2016, 17, 1578. DOI: 10.3390/ijms17091578.
[34] Chen, A.; Peng, H.; Blakey, I.; Whittaker, A. K. Biocidal
Polymers: A Mechanistic Overview. Polym. Rev. 2017, 57,
276–310. DOI: 10.1080/15583724.2016.1223131.
[35] Denisa, D.; Nikos, D. K.; Vlasoula, B.; Georgios, B.; Joannis,
K. K. Polymeric Antimicrobial Coatings Based on Quaternary
Ammonium Compounds. Coatings 2018, 8, 8–22. DOI:
10.3390/coatings8010008.
[52] Gucma, M.; Golebiewski, W. M.; Krawczyk, M. NMR Studies
on 1,3-Dipolar Cycloaddition of Nitrile Oxides to Norbornenes.

268
E. B. ERSOY ET AL.
J. Braz. Chem. Soc. 2013, 24, 805–813. DOI: 10.5935/0103-
5053.20130106.
Heterocycles 1986, 24, 1535–1538. DOI: 10.3987/R-1986-06-
1535.
[60] Rajkumar, V.; Aslam, N. A.; Reddy, C.; Babu, S. A. Unactivated
Norbornenes in [3 þ 2] Cycloadditions: Remarkably Stereo-con-
trolled Entry into Norbornane-Fused Spirooxindolopyrrolidines,
[53] Jaroskkova, L.; Fisera, L. Preparation of 2,4-Dichlorobenzoyl
Substituted Isoxazolidines. Collect. Czech. Chem. Commun.
1993, 58, 588–591. DOI: 10.1135/cccc19930588.
Spiro-1,3-indandionolylpyrrolidines,
and
[54] Fisera, L.; Pavlovic, D. 1,3-Dipolar Cycloadditions to 2,3-dime-
Spirooxindolopyrrolizidines. Synlett 2012, 4, 549–556. DOI:
10.1055/s-0031-1290342.
thoxycarbonyl-7-oxabicyclo[2,2,1]-2,5-heptadiene,
1,4-epoxy-
1,4-dihydronaphthalene, and Exo-endo-1,6-dimethoxycarbonyl-
11,12-dioxatetracyclo-[4,4,0,12,5,17,10]-3,8-Dodecadiene. Collect.
Czech. Chem. Commun.1984, 49, 1990–2000. DOI: 10.1135/
cccc19841990.
[61] Arjona, O.; Dios, A.; Pradilla, R. F.; Mallo, A.; Plumet, J. Polar
vs Steric Effects in the 1,3-dipolar Cycloaddition Reactions of
Acetonitrile Oxide and 2-endO-acetoxy-5-halo-7-oxabicy-
clo[2.2.1]hept-5-en-2-exo-Carbonitrile. Tetrahedron 1990, 46,
8179–8186. DOI: 10.1016/S0040-4020(01)81474-5.
[62] Arjona, O.; Dominguez, C.; Pradilla, R. F.; Mallo, A.; Manzano,
C.; Plumet, J. 1,3-Dipolar Cycloadditions between Nitrile
Oxides and Substituted 7-oxabicyclo[2.2.1]Heptenes. J. Org.
Chem. 1989, 54, 5883–5887. DOI: 10.1021/jo00286a018.
[63] Mayo, P.; Hecnar, T.; Tam, W. 1,3-Dipolar Cycloaddition of
Nitrile Oxides with Unsymmetrically Substituted Norbornenes.
Tetrahedron 2001, 57, 5931–5941. DOI: 10.1016/S0040-
4020(01)00573-7.
[64] Namboothiri, I. N. N.; Rastogi, N.; Ganguly, B.; Mobin, S. M.;
Cojocaru, M. Selectivities in the 1,3-Dipolar Cycloaddition of
Nitrile Oxides to Dicyclopentadiene and Its Derivatives.
Tetrahedron 2004, 60, 1453. DOI: 10.1016/j.tet.2003.12.026.
[65] Bakavoli, M.; Gholizadeh, M.; Eshghi, H.; Izadyar, M.; Tajabadi,
J. The Origin of Regio- and Stereoselectivity in 1,3-dipolar
Cycloaddition of Nitrile Oxides with C1-substituted 7- oxaben-
[55] Sasaki, T.; Eguchi, S.; Yamaguchi, M.; Esaki, T. Synthesis of
Adamantane Derivatives. 52. 1,3-Dipolar Cycloaddition
Reactions of 1-azidoadamantane. Reactivity, regioselectivity, and
Carbon-13 Nuclear Magnetic Resonance Spectra of 1-(1-ada-
mantyl)-.Delta.2-1,2,3-triazolines and -1H-1,2,3-Triazoles. J.
Org. Chem. 1981, 46, 1800–1804. DOI: 10.1021/jo00322a009.
[56] Sasaki, T.; Kanernatsu, K.; Kayakawa, K.; Vchide, M. Studies of
Bridged Benzoheterocycles. Part III. Cycloadditions of 1,4-
epoxy-1,4-dihydronaphthalene to Some Dipolar Compounds
and Dienes. J. Chem. Soc., Perkin Trans. 1972, 1, 2750–2755.
DOI: 10.1039/P19720002750.
[57] Jedlovska, E.; Fisera, L. 1,3-Dipolar Cycloadditions of
Heterocycles. 21. Cycloaddition of 2,5-dimethyl-3-furonitrile
Oxide with Cyclic and Heterocyclic-Compounds. Chem. Pap.
1991, 45, 419–426.
[58] Jedlovska, E.; Fisera, L. Preparation of 2,4-Dichlorobenzoyl-
Substituted Isoxazolines and Isoxazoles. Chem. Pap. 1992, 46,
238–243.
zonorbornadienes,
A
DFT Study. RSC Adv. 2015, 5,
38489–38498. DOI: 10.1039/C5RA04254B.
[59] Plumet, J.; Escobar, G.; Manzano, C.; Arjona, O.; Carrupt,
P. A.; Vogel, P. Regioselectivity of 1,3-Dipolar Cycloadditions
Controlled by Remote Substitution and Lewis Acid Catalysts.
[66] Mercalli, V.; Meneghetti, F.; Tron, G. C. Isocyanide-Mediated
Multicomponent Synthesis of C-Oximinoamidines. Org. Lett.
2013, 15, 5902–5905. DOI: 10.1021/ol403062m.