Р-стереогенні діамандоїдні фосфіни
Despite diamondoid phosphines have found many synthetic applications and are even available commercially the chemistry of chiral diamondoid phosphines remains largely unexplored.Aim. To develop the convenient preparative method for the preparation of sterically-congested P-stereogenic secondary diam...
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| Published in: | Журнал органічної та фармацевтичної хімії |
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| Date: | 2020 |
| Volume: | 18 |
| Issue: | 3(71) |
| Pages: | 35-38 |
| ISSN: | 2518-1548 |
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| Language: | English |
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2020
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Journal of Organic and Pharmaceutical Chemistry| _version_ | 1874455121998381056 |
|---|---|
| author | Butova, Kateryna D. Bahonsky, Vladislav V. Yurchenko, Raisa I. Butov, Sergey O. Moroz, Maryna M. Fokin, Andrey A. |
| author_facet | Butova, Kateryna D. Bahonsky, Vladislav V. Yurchenko, Raisa I. Butov, Sergey O. Moroz, Maryna M. Fokin, Andrey A. |
| author_institution_txt_mv | [
{
"author": "Kateryna D. Butova",
"institution": "НТУУ «Київський політехнічний інститут імені Ігоря Сікорського»",
"orcid": ""
},
{
"author": "Vladislav V. Bahonsky",
"institution": "Гіссенський університет імені Юстуса Лібіха",
"orcid": ""
},
{
"author": "Raisa I. Yurchenko",
"institution": null,
"orcid": ""
},
{
"author": "Sergey O. Butov",
"institution": "НТУУ «Київський політехнічний інститут імені Ігоря Сікорського»",
"orcid": ""
},
{
"author": "Maryna M. Moroz",
"institution": "НТУУ «Київський політехнічний інститут імені Ігоря Сікорського»",
"orcid": ""
},
{
"author": "Andrey A. Fokin",
"institution": "НТУУ «Київський політехнічний інститут імені Ігоря Сікорського»",
"orcid": ""
}
] |
| author_sort | Butova, Kateryna D. |
| baseUrl_str | https://ophcj.nuph.edu.ua/oai |
| collection | OJS |
| container_end_page | 38 |
| container_issue | 3(71) |
| container_start_page | 35 |
| container_title | Журнал органічної та фармацевтичної хімії |
| container_volume | 18 |
| datestamp_date | 2026-08-24T17:15:07Z |
| description | Despite diamondoid phosphines have found many synthetic applications and are even available commercially the chemistry of chiral diamondoid phosphines remains largely unexplored.Aim. To develop the convenient preparative method for the preparation of sterically-congested P-stereogenic secondary diamodoidyl phosphines as potential organocatalysts and ligands in the asymmetric synthesis.Results and discussion. A convenient method for the synthesis of P-stereogenic diamondoid phosphines with high yields through the phosphorylation of hydroxydiamondoids in trifluoroacetic acid followed by the reduction of the corresponding asymmetric chlorophosphonates has been proposed. The secondary phosphines obtained form stable complexes with borane that can be used to separate diamondoid phosphines into enantiomers.Experimental part. The experimental procedures for the preparation of 1- and 4-diamantyl-1-adamantyl- and phenylphosphines were developed; the structures of new compounds were confirmed by NMR and HRMS spectral data.Conclusions. A number of P-stereogenic mixed diamondoidylaryl phosphines and the secondary phosphines containing exclusively diamondoid substituents has been prepared. A degree of steric bulkiness is determined by the combination of diamondoid substituents around a phosphorus atom where 1-diamantyl derivatives are the most sterically-congested. The compounds obtained are potential ligands in asymmetric catalysis.Received: 31.03.2020Revised: 24.06.2020Accepted: 27.08.2020 |
| doi_str_mv | 10.24959/ophcj.20.199828 |
| first_indexed | 2025-07-17T13:00:44Z |
| format | Article |
| fulltext |
Журнал органічної та фармацевтичної хімії. – 2020. – Т. 18, вип. 3 (71)
35
ISSN 2518-1548 (Online) ISSN 2308-8303 (Print)
UDC 547.316+54.057 https://doi.org/10.24959/ophcj.20.199828
E. D. Butova1, V. V. Bahonsky1,2, R. I. Yurchenko1, S. O. Butov1,
M. M. Moroz1, A. A. Fokin1
1 National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Ukraine
37, Peremohy Ave., Kyiv, 03056, Ukraine. E-mail: ebutova@yahoo.com
2 Justus Liebig University Giessen, Germany
P-Stereogenic diamondoid phosphines
Despite diamondoid phosphines have found many synthetic applications and are even available commer-
cially the chemistry of chiral diamondoid phosphines remains largely unexplored.
Aim. To develop the convenient preparative method for the preparation of sterically-congested P-stereogenic
secondary diamodoidyl phosphines as potential organocatalysts and ligands in the asymmetric synthesis.
Results and discussion. A convenient method for the synthesis of P-stereogenic diamondoid phosphines
with high yields through the phosphorylation of hydroxydiamondoids in trifluoroacetic acid followed by the re-
duction of the corresponding asymmetric chlorophosphonates has been proposed. The secondary phosphines
obtained form stable complexes with borane that can be used to separate diamondoid phosphines into enan-
tiomers.
Experimental part. The experimental procedures for the preparation of 1- and 4-diamantyl-1-adamantyl-
and phenylphosphines were developed; the structures of new compounds were confirmed by NMR and HRMS
spectral data.
Conclusions. A number of P-stereogenic mixed diamondoidylaryl phosphines and the secondary phos-
phines containing exclusively diamondoid substituents has been prepared. A degree of steric bulkiness is deter-
mined by the combination of diamondoid substituents around a phosphorus atom where 1-diamantyl derivatives
are the most sterically-congested. The compounds obtained are potential ligands in asymmetric catalysis.
Key words: phosphine borane complexes; 1-adamantyldiamantylphosphine;
4-adamantyldiamantylphosphine; 1-phenyldiamantylphosphine; 4-phenyldiamantylphosphine; P-stereogenic
phosphines
К. Д. Бутова1, В. В. Бахонський1,2, Р. І. Юрченко1, С. О. Бутов1,
М. М. Мороз1, А. А. Фокін1
1 НТУУ «Київський політехнічний інститут імені Ігоря Сікорського», Україна
2 Гіссенський університет імені Юстуса Лібіха, Німеччина
Р-стереогенні діамандоїдні фосфіни
Незважаючи на те, що діамандоїдні фосфіни широко використовуються в органічному синтезі і навіть
доступні комерційно, хімія хіральних діамандоїдних фосфінів залишається не дослідженою.
Мета. Розробити зручний препаративний метод синтезу стереоускладнених Р-стереогенних вторин-
них діамандоїдних фосфінів, які можуть бути використані як ліганди в асиметричному синтезі, а також як
органокаталізатори.
Результати та їх обговорення. Запропоновано зручний метод синтезу P-стереогенних діамандоїдних
фосфінів шляхом фосфорилювання гідроксипохідних діамандоїдів у трифтороцтовій кислоті з подальшим
відновленням відповідних асиметричних хлорофосфонатів з високими виходами. Одержані таким чином
фосфіни утворюють стійкі комплекси з бораном, які розглядаються як проміжні сполуки для подальшого
розділення енантіомерів.
Експериментальна частина. Був розроблений препаративний метод синтезу 1- і 4-діамантил-, 1-ада-
мантил- і фенілфосфінів, структури яких підтверджено мас-спектрометричними і ЯМР-спектральними да-
ними.
Висновки. Одержано ряд Р-стереогенних змішаних діамандоїларилфосфінів та вторинних фосфінів,
які містять виключно діамандоїдні замісники. Ступінь стеричного навантаження сполук визначається ком-
бінацією діамандоїдних замісників навколо атома фосфору, де похідні 1-діамантилу найбільш стерично
ускладнені. Одержані сполуки є потенційними лігандами в асиметричному каталізі.
Ключові слова: боранові комплекси фосфінів; 1-адамантилдіамантилфосфін;
4-адамантилдіамантилфосфін; 1-фенілдіамантилфосфін; 4-фенілдіамантилфосфін; Р-стереогенні
фосфіни
Copyright © 2020, E. D. Butova, V. V. Bahonsky, R. I. Yurchenko, S. O. Butov, M. M. Moroz, A. A. Fokin
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0)
Organophosphorus compounds are among useful
ligands in catalysts where further progress is largely
associated with P-stereogenic phosphines as stated
by W. Knowles in his Nobel Lecture: “…if one wanted
to get high values, the asymmetry would have to be di-
rectly on the phosphorus” [1]. Accordingly, over the last
decades many chiral tertiary phosphines trademar-
ked as Quinox-P, Benz-P, Pincer-P, and some
others [2] become available commercially. These li-
gands allow obtaining high yields and enantiomeric
Journal of Organic and Pharmaceutical Chemistry. – 2020. – Vol. 18, Iss. 3 (71)
36
ISSN 2308-8303 (Print) ISSN 2518-1548 (Online)
excesses of products in various transformations in-
volving hydroacylations [3, 4], catalytic asymmetric
hydrogenations [5, 6] and many others [7].
Achiral bulky diadamantyl alkyl phosphines have been
introduced as effective ligands where Ad2P(nBu) and
Ad2PBn are now commercially available as cataCXiumA
and cataCXiumABn, respectively. The palladium complex
with Ad2P(nBu) as a ligand acts as a highly efficient
catalyst in Suzuki reactions for aryl chlorides [8], in
the arylation reactions [9], in Buchwald−Hartwig
coupling [10] and for the arylations of ketones [11].
The Na2PdCl4/Ad2PBn system has been successfully
applied for the Sonogashira coupling [12]. Extremely
bulky Ad3P in the presence of palladium acetate was
recently used as a catalyst for the arylation of unsa-
turated cyclic ketoethers [13]. The chemistry of chiral
diamondoid phosphines still remains almost unex-
plored. Only recently the rhodium complex of di-1-ada-
mantylphosphino-(tert-butylmethylphosphino)me-
thane (BulkyP*) was prepared and tested as a ligand
for Rh-promoted asymmetric hydrogenations of
functionalized alkenes where effective transforma-
tions were achieved under very low catalyst loadings
(< 0.001 mol %) [14].
All above makes important the preparation of P-ste-
reogenic diamondoid phosphines since the incorpo-
ration of bulky substituents into phosphine may en-
hance the catalytic activity and selectivity of the ca-
talyst. Previously, we prepared a number of P-stereo-
genic mixed diamondoidylaryl phosphines [15]. In this
paper we present the preparation of the secondary
diamondoid phosphines with the potential as ligands
in asymmetric catalysis.
Results and discussion
The aim of this work was to develop a prepara-
tive method for the synthesis of chiral bulky phos-
phines containing phenyl, adamantyl, and diamantyl
groups. The key starting compounds – 1-hydroxydia-
mantane 2a and 4-hydroxydiamantane 2b were pre-
pared from diamantane 1 through the nitroxylation
with the concentrated nitric acid and further acidic
hydrolysis as previously described [16] (Scheme 1).
Hydroxydiamantanes 2a,b were converted to the cor-
responding chlorophosphonates 3ad, 3bd, 3ac, and
3bc through the phosphorylation reaction in trifluo-
roacetic acid [17, 18] utilizing PhPCl2 and AdPCl2 as
phosphorylating agents (Scheme 2). Chlorophospho-
nates 3ad, 3bd, 3ac, and 3bc were further reduced
with LiAlH4 in tetrahydrofuran to give phosphines 4ad,
4bd, 4ac, and 4bc. Stability towards oxygen is an im-
portant factor that determines the practical poten-
tial of phosphine ligands. In contrast to the primary
diamondoid phosphines that were reactive towards
oxygen, the secondary diamondoid phosphines even
with one diamantyl group (4ac and 4bc) were quite
persistent towards oxidation. Nevertheless, for puri-
fications via column chromatography phosphines 4ad,
4bd, 4ac, and 4bc were converted into boron comp-
lexes 5ad, 5bd, 5ac, and 5bc in the BH3/THF system.
The structures of the phosphines obtained we-
re proven by a number of spectral characteristics.
The 13C NMR DEPT 135 spectrum of 4-diamantyl-
1-adamantylphosphine borane 5bd contained four
CH2, four CH, and two C resonances. It agrees with
the axial symmetry of diamondoid fragments. In cont-
rast, the 13C NMR spectrum of 5ad contained ten re-
sonances of the prochiral 1-diamantyl moiety due to
the presence of the chiral P-center in the structure.
The NMR spectra of complexes 5ac and 5bc displa-
yed a dynamic behavior and were measured under
cooling.
The borane protecting group can further be remo-
ved either by the treatment with excess of diethyl-
amine [19] or, more conveniently, using pyrrolidine
[20] under mild reaction conditions that retain the ab-
solute configuration of the P-stereogenic center.
Experimental part
NMR spectra were recorded on a Bruker Avance III
spectrometer at 400 and 600 MHz (for 1H, the fre-
quencies for 13C and 31P NMR are specified below)
OH
1. HNO3
OH
+
2. H2SO4, H2O
3. Chromatographic
separation
1 2a 2b
Scheme 1. The synthesis of 1- and 4-hydroxydiamantanes
P
O
Cl P
H
BH3/THF P
BH3
2a,b 3ad (76%)
3bd (92%)
3ac (34%)
3bc (45%)
R1PCl2
F3CCOOH
LiAlH4
OH
a: 1-diamantyl
b: 4-diamantyl
c: R1 = , d: R1 =
H
R1 R1 R1
4ad (80%)
4bd (85%)
4ac (40%)
4bc (43%)
5ad (96%)
5bd (95%)
5ac (95%)
5bc (95%)
Scheme 2. The synthesis of borane complexes of 1- and 4-diamantyl-1-adamantyl phosphines and 1- and 4-diamantylphenyl phosphines
Журнал органічної та фармацевтичної хімії. – 2020. – Т. 18, вип. 3 (71)
37
ISSN 2518-1548 (Online) ISSN 2308-8303 (Print)
with TMS (1H and 13C) and H3PO4 (31P) as internal
standards. High-resolution mass spectra (HRMS) were
recorded using an ESI-MS Bruker Mikro-TOF spectro-
meter. Products were purified by chromatography on
100 − 160 mesh silica gel. Commercially available rea-
gents (Aldrich) and solvents were used after standard
purification procedures. Melting points were measu-
red in sealed capillaries on Krüss KSP1N.
The synthesis of 1-adamantyl-P,P-dichloro-
phosphine.To the mixture of adamantane (100.0 g,
0.735 mol) and anhydrous AlCl3 (120.3 g, 0.904 mol)
in a 1000 mL Schlenk flask add 100 mL (1.14 mol) of
PCl3 via a syringe, and reflux the reaction mixture for
3.5 h at 75‒80 °C. Add pyridine (116.0 g, 1.48 mol)
dropwise, reflux the mixture for additional 0.5 h. Cool
the mixture, add 200 mL of heptane, and reflux the sus-
pension for 15 min, cool to the room temperature,
decant the solvent (repeat the operation 3 times).
Evaporate the combined heptane extracts under va-
cuum. Vacuum distillation (5·10−3 mbar, b.p. 75 °C)
gave AdPCl2 as a white solid. 31P NMR (162 MHz, CDCl3),
δ, ppm: 192.1, (lit. 192.1 ppm [21]).
The general procedure for the preparation of
chlorophosphonates 3. To the corresponding hyd-
roxydiamantane (2.0 g, 9.8 mmol) and 85 mL of tri-
fluoroacetic acid add AdPCl2 (7.0 g, 30 mmol). Reflux
the reaction mixture for 5 h, cool, pour onto ice (200 mL),
and filter. Wash the precipitate with water and dry.
Purify the crude product by column chromatography
on silica (hexane − diethyl ether (2:1)) to give the cor-
responding diamantyl-1-adamantyl chlorophospho-
nate as colorless crystals. The NMR spectra of chlo-
rophosphonates 3ac and 3bc were identical as pre-
viously described [18].
1-Diamantyl-1-adamantylchlorophosphona-
te 3ad. M. p. 265 °C. 1H NMR (400 MHz, CDCl3), δ, ppm:
1.49 (1H, d, J = 20 Hz), 1.52 (1H, d, J = 20 Hz), 1.63 − 1.81
(15H, m,), 1.85 − 2.01 (4H, m), 2.04 − 2.10 (3H, m), 2.13 − 2.27
(6H, m), 2.32 − 2.45 (2H, m), 2.93 (1H, d, J = 20 Hz),
3.04 (1H, d, J = 20 Hz). 13C NMR (100 MHz, CDCl3),
δ, ppm: 25.0 (CH), 25.8 (CH, d, J(C−Р) = 12 Hz), 28.1
(CH, d, J(C−Р) = 11 Hz), 33.0 (CH2), 34.1 (CH2), 36.3
(CH2, d, J(C−Р) = 1.7 Hz), 36.9 (CH2, d, J(C−Р) = 1.9 Hz),
37.1 (CH2, d, J(C−Р) = 2.6 Hz), 37.5 (CH, d, J(C−Р) = 2 Hz),
37.6 (CH2), 37.8 (CH, d, J(C−Р) = 12 Hz), 38.6 (CH2),
38.9 (CH2), 39.1 (CH, d, J(C−Р) = 10 Hz), 39.2 (CH, d,
J(C−Р) = 12 Hz), 39.5 (CH), 47.6 (C, d, J(C−Р) = 56 Hz),
52.5 (C, d, J(C−Р) = 51 Hz). 31P{1H} NMR (162 MHz,
CDCl3), δ, ppm: 87.23. HRMS (EI), m/z: calcd. for
C24H34ClOP 404.2036; found 404.2030.
4-Diamantyl-1-adamantylchlorophosphona-
te 3bd. Yield − 92 %. M. p. 285 °C. 1H NMR (400 MHz,
CDCl3), δ, ppm: 1.69 − 1.85 (17H, m), 1.86 − 1.95 (3H, m),
2.05 − 2.10 (3H, m), 2.15 − 2.25 (11H, m). 13C NMR
(100 MHz, CDCl3), δ, ppm: 25.4 (CH), 27.8 (CH, d,
J(C−Р) = 11 Hz), 36.3 (CH), 36.4 (CH2), 36.9 (CH2),
37.0 (CH), 37.5 (CH2, d, J(C−Р) = 1.6 Hz), 37.9 (CH2, d,
J(C−Р) = 1.9 Hz), 43.8 (C, d, J(C−Р) = 60 Hz), 45.7 (C, d,
J(C−Р) = 60 Hz). 31P{1H} NMR (162 MHz, CDCl3), δ, ppm:
87.0. HRMS (EI), m/z: calcd. for C24H34ClOP 404.2036
[M+]; found 404.2029.
The general procedure for the preparation of
phosphine-borane complexes 5. Add the solution
of chlorophosphonate 3 (9.6 mmol) in dry THF (20 mL)
to LiAlH4 (0.2 g, 5.26 mmol) stirred in dry THF (40 mL).
Reflux the reaction mixture for 1 − 2 h, cool, then add
35 % HCl (15 mL), and extract the mixture with chloro-
form (3 × 15 mL). Wash the combined extracts with
water (10 mL) and dry over Na2SO4. After removing
the solvent dissolve residue in 20 mL of THF; add
slowly the BH3–THF complex (25 mL, 1.01 M in THF,
25 mmol) at room temperature, and stir the result-
ing mixture for 2.5 h at this temperature. Remove
the solvent in vacuum. Purify the residue by column
chromatography on silica (CH2Cl2) to give phosphine-
borane complex 5 as a colorless solid.
1-Diamantyl-1-adamantylphosphine-borane 5ad.
Yield − 96 %. M. p. 201 − 202 °C. 1H NMR (600 MHz,
CDCl3), δ, ppm: 0.25 − 0.75 (3Н, m), 1.12 − 1.18 (1H, m),
1.21 − 1.29 (1H, m), 1.50 − 1.60 (18H, m), 1.75 − 1.90
(10H, m), 2.00 − 2.25 (4H, m), 4.8 (1Н, d, J(Р−Н) = 354 Hz).
13C NMR (151 MHz, CDCl3), δ, ppm: 25.3 (CH), 25.9
(CH, d, J(C−Р) = 10 Hz), 28.2 (CH, d, J(C−Р) = 9 Hz),
32.8 (CH2), 33.4 (CH2), 34.8 (C, d, J(C−Р) = 28 Hz),
36.4 (CH2), 37.0 (CH), 37.1 (CH2), 37.6 (CH), 38.0 (CH2),
38.2 (CH, d, J(C−Р) = 9 Hz), 38.4 (CH, d, J(C−Р) = 6 Hz),
38.6 (CH, d, J(C−Р) = 8 Hz), 38.6 (CH2), 40.3 (CH2),
40.3 (CH2), 41.3 (C, d, J(C–Р) = 22 Hz). 31P{1H} NMR
(243 MHz, CDCl3): δ, ppm: 11.61 (d, J(Р−Н) = 354 Hz).
HRMS (EI), m/z: calcd. for C24H38BP 391.2702 [M+Na]+;
found 391.2704.
4-Diamantyl-1-adamantylphosphine-borane 5bd.
Yield − 95 %. M. p. 226 − 228 °C. 1H NMR (400 MHz,
CDCl3), δ, ppm: 0.16 − 0.83 (3Н, m), 1.85 − 1.70 (19H,
m), 2.05 − 1.90 (15H, m), 3.76 (1Н, d, J(H−Р) = 370 Hz).
13C NMR (100 MHz, CDCl3), δ, ppm: 25.4 (CH), 28.1
(CH, d, J(C−Р) = 10 Hz), 32.6 (C, d, J(C−Р) = 28 Hz),
34.6 (C, d, J(C−Р) = 2 Hz), 36.4 (CH), 36.4 (CH2), 37.3
(CH, d, J(C−Р) = 10 Hz), 37.8 (CH2, d, J(C−Р) = 1.4 Hz),
40.0 (CH2), 40.5 (CH2). 31P{1H} NMR (162 MHz, CDCl3),
δ, ppm: 39.6 (d, J(Р−Н) = 370 Hz). HRMS (EI), m/z:
calcd. for C24H38BP 391.2702 [M+Na]+; found 391.2705.
4-Diamantylphenylphosphine-borane 5bc. Yield −
85 %. M. p. 175 °C. 1H NMR (600 MHz, 223 K, CDCl3),
δ, ppm: 0.75 − 1,25 (3Н, m), 1.45 − 1.88 (19H, m), 4.95
(1H, d, J(H−P) = 390 Hz), 7.41 − 7.45 (2H, m), 7.46 − 7.48
(1H, m), 7.55 − 7.65 (2H, m). 13C NMR (100 MHz, 248 K,
CDCl3, δ, ppm): 25.3 (CH), 29.4 (C, d, J(C−Р) = 33 Hz),
36.6 (CH2), 37.0 (CH2, d, J(C−Р) = 10 Hz), 37.5 (CH, d,
J(C−Р) < 1 Hz), 38.8 (CH), 123.8 (C, d, J(C−Р) = 51 Hz),
128.4 (CH, d, J(C−Р) = 9 Hz), 131.4 (C, d, J(C−Р) = 8 Hz);
134.2 (CH, d, J(C−Р) = 8 Hz). 31P{1H} NMR (243 MHz,
245K, CDCl3), δ, ppm: 26.9. HRMS (EI), m/z: calcd. for
C20H28PB 310.2022 [M]+; found 310.2025.
Journal of Organic and Pharmaceutical Chemistry. – 2020. – Vol. 18, Iss. 3 (71)
38
ISSN 2308-8303 (Print) ISSN 2518-1548 (Online)
1-Diamantylphenylphosphine-borane 5ac. Yield −
75 %. M. p. 147 − 148 °C. 1H NMR (400 MHz, 253 K, CDCl3),
δ, ppm: 0.20 − 1.20 (3H, m), 1.55 − 1.61 (1H, m), 1.70 − 1.75
(1H, m), 1.75 − 1.90 (12Н, m), 1.91 − 2.20 (3H, m), 2.30 − 2.37
(1H, m), 2.49 − 2.62 (1H, m), 6.09 (1H, d, J(H−P) = 390 Hz),
7.45 − 7.48 (2H, m), 7.52 − 7.62 (1H, m), 7.85 − 7.91 (2H, m).
13C NMR (100 MHz, 253 K, CDCl3), δ, ppm: 25.7 (CH),
25.8 (CH, d, J(C−Р) = 4 Hz), 32.8 (CH2), 35.5 (CH2, d, J(C−Р) =
= 10 Hz), 36.2 (CH, d, J(C−Р) = 6 Hz), 36.6 (CH, d, J(C−Р) =
= 3 Hz), 36.9 (CH), 37.1 (CH2), 37.4 (CH2), 37.5 (C), 37.8 (CH,
d, J(C−Р) = 9 Hz), 38.0 (CH, d, J(C−Р) = 7 Hz), 38.6 (CH2, d,
J(C−Р) = 2 Hz), 123.9 (C, d, J(C−Р) = 54 Hz), 128.6 (CH, d,
J(C−Р) = 9.5 Hz), 131.4 (CH, d, J(C−Р) = 2.5 Hz), 134.6 (CH,
d, J(C−Р) = 7.3 Hz). 31P{1H} NMR (162 MHz, 293 K, CDCl3),
δ, ppm: −3.19 (d, J(P−H) = 390 Hz). HRMS (EI), m/z:
calcd. for C20H28PB 310.2022 [M]+; found 310.2028.
Conclusions
Rigid diamondoidyl groups with controlled bul-
kiness are a promising building block in asymmetric
catalysts. A convenient method for the synthesis of
1- and 4-diamantyl P-stereogenic phosphines with high
yields from the corresponding chlorophosphonates
has been proposed. These compounds with control-
led topology are potential ligands for the asymmet-
ric synthesis as organocatalysts. The borane comp-
lexes of the secondary diamondoid phosphines are
subjected for further enantioseparation through di-
astereomeric derivatives that is currently underway
in our laboratories.
Conflict of interests: authors have no conflict of
interests to declare.
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Received: 31. 03. 2020
Revised: 24. 06. 2020
Accepted: 27. 08. 2020
Acknowledgements
We are grateful to Prof. Dr. Peter R. Schreiner and Dr. Heike Hausmann (Institute of Organic Chemistry, University Giessen)
for their assistance with spectral studies.
The research was carried out according to the agreement No. 1400/26-Н “Synthesis of new nanocarbon materials on the basis
of stereocomplicated organic compounds. Development of prototypes and research of their physical and chemical properties”
(customer: “Innovative research and production enterprise “UKRTECHNANO””).
|
| id | oai:ojs.journals.uran.ua:article-199828 |
| institution | Journal of Organic and Pharmaceutical Chemistry |
| issn | 2518-1548 |
| keywords_txt_mv | |
| language | English |
| last_indexed | 2026-08-25T01:01:47Z |
| publishDate | 2020 |
| publisher | National University of Pharmacy |
| record_format | ojs |
| resource_txt_mv | ophcjnupheduua/3a/70f3fb30607264445c92b55751d6e63a.pdf |
| spelling | oai:ojs.journals.uran.ua:article-1998282026-08-24T17:15:07Z P-Stereogenic diamondoid phosphines Р-стереогенні діамандоїдні фосфіни Butova, Kateryna D. Bahonsky, Vladislav V. Yurchenko, Raisa I. Butov, Sergey O. Moroz, Maryna M. Fokin, Andrey A. phosphine borane complexes 1-adamantyldiamantylphosphine 4-adamantyldiamantylphosphine 1-phenyldiamantylphosphine 4-phenyldiamantylphosphine P-stereogenic phosphines 547.316 54.057 боранові комплекси фосфінів 1-адамантилдіамантилфосфін 4-адамантилдіамантилфосфін 1-фенілдіамантилфосфін 4-фенілдіамантилфосфін Р-стереогенні фосфіни 547.316 54.057 Despite diamondoid phosphines have found many synthetic applications and are even available commercially the chemistry of chiral diamondoid phosphines remains largely unexplored.Aim. To develop the convenient preparative method for the preparation of sterically-congested P-stereogenic secondary diamodoidyl phosphines as potential organocatalysts and ligands in the asymmetric synthesis.Results and discussion. A convenient method for the synthesis of P-stereogenic diamondoid phosphines with high yields through the phosphorylation of hydroxydiamondoids in trifluoroacetic acid followed by the reduction of the corresponding asymmetric chlorophosphonates has been proposed. The secondary phosphines obtained form stable complexes with borane that can be used to separate diamondoid phosphines into enantiomers.Experimental part. The experimental procedures for the preparation of 1- and 4-diamantyl-1-adamantyl- and phenylphosphines were developed; the structures of new compounds were confirmed by NMR and HRMS spectral data.Conclusions. A number of P-stereogenic mixed diamondoidylaryl phosphines and the secondary phosphines containing exclusively diamondoid substituents has been prepared. A degree of steric bulkiness is determined by the combination of diamondoid substituents around a phosphorus atom where 1-diamantyl derivatives are the most sterically-congested. The compounds obtained are potential ligands in asymmetric catalysis.Received: 31.03.2020Revised: 24.06.2020Accepted: 27.08.2020 Незважаючи на те, що діамандоїдні фосфіни широко використовуються в органічному синтезі і навіть доступні комерційно, хімія хіральних діамандоїдних фосфінів залишається не дослідженою.Мета. Розробити зручний препаративний метод синтезу стереоускладнених Р-стереогенних вторинних діамандоїдних фосфінів, які можуть бути використані як ліганди в асиметричному синтезі, а також як органокаталізатори.Результати та їх обговорення. Запропоновано зручний метод синтезу P-стереогенних діамандоїдних фосфінів шляхом фосфорилювання гідроксипохідних діамандоїдів у трифтороцтовій кислоті з подальшим відновленням відповідних асиметричних хлорофосфонатів з високими виходами. Одержані таким чином фосфіни утворюють стійкі комплекси з бораном, які розглядаються як проміжні сполуки для подальшого розділення енантіомерів.Експериментальна частина. Був розроблений препаративний метод синтезу 1- і 4-діамантил-, 1-адамантил- і фенілфосфінів, структури яких підтверджено мас-спектрометричними і ЯМР-спектральними даними.Висновки. Одержано ряд Р-стереогенних змішаних діамандоїларилфосфінів та вторинних фосфінів, які містять виключно діамандоїдні замісники. Ступінь стеричного навантаження сполук визначається комбінацією діамандоїдних замісників навколо атома фосфору, де похідні 1-діамантилу найбільш стерично ускладнені. Одержані сполуки є потенційними лігандами в асиметричному каталізі.Received: 31.03.2020 Revised: 24.06.2020 Accepted: 27.08.2020 National University of Pharmacy 2020-09-18 Article Article application/pdf https://ophcj.nuph.edu.ua/article/view/ophcj.20.199828 10.24959/ophcj.20.199828 Journal of Organic and Pharmaceutical Chemistry; Vol. 18 No. 3(71) (2020); 35-38 Журнал органической и фармацевтической химии; Том 18 № 3(71) (2020); 35-38 Журнал органічної та фармацевтичної хімії; Том 18 № 3(71) (2020); 35-38 2518-1548 2308-8303 en https://ophcj.nuph.edu.ua/article/view/ophcj.20.199828/212733 Copyright (c) 2020 Kateryna D. Butova, Vladislav V. Bahonsky, Raisa I. Yurchenko, Sergey O. Butov, Maryna M. Moroz, Andrey A. Fokin https://creativecommons.org/licenses/by/4.0 |
| spellingShingle | боранові комплекси фосфінів 1-адамантилдіамантилфосфін 4-адамантилдіамантилфосфін 1-фенілдіамантилфосфін 4-фенілдіамантилфосфін Р-стереогенні фосфіни 547.316 54.057 Butova, Kateryna D. Bahonsky, Vladislav V. Yurchenko, Raisa I. Butov, Sergey O. Moroz, Maryna M. Fokin, Andrey A. Р-стереогенні діамандоїдні фосфіни |
| title | Р-стереогенні діамандоїдні фосфіни |
| title_alt | P-Stereogenic diamondoid phosphines |
| title_full | Р-стереогенні діамандоїдні фосфіни |
| title_fullStr | Р-стереогенні діамандоїдні фосфіни |
| title_full_unstemmed | Р-стереогенні діамандоїдні фосфіни |
| title_short | Р-стереогенні діамандоїдні фосфіни |
| title_sort | р-стереогенні діамандоїдні фосфіни |
| topic | боранові комплекси фосфінів 1-адамантилдіамантилфосфін 4-адамантилдіамантилфосфін 1-фенілдіамантилфосфін 4-фенілдіамантилфосфін Р-стереогенні фосфіни 547.316 54.057 |
| topic_facet | phosphine borane complexes 1-adamantyldiamantylphosphine 4-adamantyldiamantylphosphine 1-phenyldiamantylphosphine 4-phenyldiamantylphosphine P-stereogenic phosphines 547.316 54.057 боранові комплекси фосфінів 1-адамантилдіамантилфосфін 4-адамантилдіамантилфосфін 1-фенілдіамантилфосфін 4-фенілдіамантилфосфін Р-стереогенні фосфіни 547.316 54.057 |
| url | https://ophcj.nuph.edu.ua/article/view/ophcj.20.199828 |
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