Synthesis of Anti-Cis-Phosphiranes

Article abstract of DOI:10.1080/10426507.2014.979988

A method for the preparation of three-membered phosphoric heterocycles-phosphi-ranes by reaction of dilithium derivatives of tertiary phosphines with tetrachloromethane is described. The reaction is stereoselective and leads to the formation of anti-cis(meso)-2,3-diphenylphosphiranes. Phosphiranes were isolated as individual compounds and their structure was confirmed by ¹H, ¹³C, and ³¹P NMR spectra, and mass spectra. The present method is simple and can be successfully used for the preparation of some types of phosphiranes that are inaccessible by other methods.

Full text of DOI:10.1080/10426507.2014.979988

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Phosphorus, Sulfur, and Silicon and the Related
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Synthesis Of Anti-Cis-Phosphiranes
Оlga О. Kolodiazhnaa & Oleg I. Kolodiazhnyia
a Institute of Bioorganic Chemistry and Petrochemistry of National Academy of Sciences of
Ukraine,Kiev, Murmanska Street, 1 Ukraine, 02094
Accepted author version posted online: 09 Mar 2015.
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Synthesis Of Anti-Cis-Phosphiranes
Оlga О. Kolodiazhna, Oleg I. Kolodiazhnyi*
Institute of Bioorganic Chemistry and Petrochemistry of National Academy of Sciences of
Ukraine, Ukraine, 02094, Kiev, Murmanska Street, 1
Abstract A method for the preparation of three-membered phosphoric heterocycles -
phosphiranes by reaction of dilithium derivatives of tertiary phosphines with tetrachloromethane
is described. The reaction is stereoselective and leads to the formation of anti-cis(meso)-2,3-
diphenylphosphiranes. Phosphiranes were isolated as individual compounds and their structure
1
13
was confirmed by Н, С, and 31Р NMR spectra, and mass-spectra. The present method is
simple and can be successfully used for the preparation of some types of phosphiranes that are
inaccessible by other methods
Keywords Phosphiranes, tertiary phosphines, P-chloroylides, dicarbanions of tertiary phosphines
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INTRODUCTION
Phosphiranes represent an interesting type of three-membered phosphorous heterocycles
that attracts attention from a practical and theoretical viewpoint. The first phosphiranes, which
included the parent compound, were described by Wagner in two patents issued in 1963.1a,b
Although initially viewed with some skepticism, their discovery was fully confirmed by Wagner
in an article published in 1967.2,3 Shortly thereafter, phosphiranes were intensively studied,4 on
their basis were prepared ligands for complexes of transition metals, some of which have
displayed interesting catalytic properties.5,6
In general phosphiranes are not stable, however stabilization of phosphiranes can be attained by
complexation with transition metals and the introduction of bulky substituents at phosphorus.3-6
Therefore the development of new methods for the synthesis of phosphiranes represents
indubitable interest, more so given, that this type of compound is insufficiently studied.
At present several convenient methods for the synthesis of phosphiranes have been developed.
Nieсke has proposed a method for the synthesis of phosphiranes by the reaction of
phosphaalkenes and phosphaalkynes with various carbenes.7,8 For example, diazoalkanes were
used as carbene sources. It was discovered that this reaction includes several steps and the 4p-
electrocyclic closure of the intermediate bis(methylene)phosphorane is conrotatory according to
the Woodward-Hoffmann rules.9,10 Similarly, alkylidenediazaphospholes have served as sources
of alkylidenephosphiranes, various other sources of carbenes were successfully applied for the
preparation of phosphiranes, including organometallic carbenoids and bis-ylides (Scheme 1).11-15
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RESULTS AND DISCUSSION
In present work we propose a method for the preparation of phosphiranes via the
formation of dilithium derivatives of tertiary phosphines and their subsequent reaction with
tetrachloromethane, as shown in Scheme 2. A short preliminary communication on this topic was
earlier published by us.16a The method is rather simple and can be used for the synthesis of some
types of phosphiranes, that are inaccessible by other methods. Initial tertiary phosphines 2 can be
easily prepared in high yields (70-90%) by reaction of phosphorus (III) chlorides 1 with Grignard
reagents.16a-d
The lithiation of tertiary dibenzylphosphines 2a-c with butyllithium occurs in the
presence of tetramethylethylenediamine (TMEDA) with formation of red colored solutions of
lithium 3a-c and dilithium derivatives 4a-c of tertiary phosphines. The reaction of tertiary
phosphines 2a-c with one equivalent of butyllithium afforded monolithium derivatives 3a-c, and
the reaction with double excess of butyllithium in the presence of TMEDA on heating in hexane
led to the formation of dilithium derivatives 4a-c (Scheme 3).
The reaction of tertiary dibenzylphosphines 2a-c with butyllithium is accompanied by a
red coloration of reaction mixture indicating the formation of benzyl carbanions. It is known that
lithium derivatives of benzyl carbanions are, as a rule, red in color, due to delocalization of the
31
negative charge by the benzene ring. The lithium derivatives 3,4 can be detected by Р NMR
spectra. Thus, phosphorus-31 nuclear magnetic resonance chemical shifts of monolithium
derivatives 3 are displaced upfield by 13-15 ppm, and chemical shifts P of dilithium derivatives
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4 by 35-40 ppm in relation to P of the initial tertiary phosphines 2. For example, the treatment of
tert-butyl-dibenzylphosphine (2a, P = 11.3 ppm) with one equivalent of butyllithium afforded
monolithium tertiary phosphine 3a, which was registered by signal P = –1.5 ppm. The heating of
tertiary phosphine 2a with twofold excess of butyllithium and TMEDA in hexane resulted in the
formation of dilithium derivate 4a, with signal P = 25 ppm. Similarly, the lithiation of
tribenzylphosphine 2c (P = 12 ppm) leads to the formation of dicarbanion 4с with chemical
shift P = 51 ppm. The treatment of lithium derivates 3,4 by aqueous solution of ammonium
chloride regenerates the initial tertiary phosphines. The monolithium derivative 3а reacted with
tetrachloromethane with the formation of P-chloroylide 5, registered by 31Р NMR spectrum
showing the characteristic signal for this type of compounds, P 73 ppm.17,18 The subsequent
reaction of P-chloroylide 5 with methanol led to the corresponding phosphine oxide 7 in high
yield. The reaction of dilithium derivatives with tetrachloromethane leads to the formation of
phosphiranes 8. The reaction occurred at70oC with a change of the color of the solution from
red to yellow. In 31Р NMR spectra, signals belonging to e lithium derivatives of tertiary
phosphines disappeared and new signals appeared at 100~ 180 ppm, that are characteristic for
phosphiranes. The reaction proceeds probably via the formation of P-chloroylide intermediate 6,
similarly to the reaction of monolithium substituted tertiary phosphines 3 with
tetrachloromethane. Then P-chloroylides 6 with the elimination of lithium chloride were
converted into bis(alkylidene)phosphoranes 9, which cyclized with the formation of
phosphiranes. We have not detected the bis(alkylidene)phosphoranes 9 by NMR spectra, because
they are unstable and easily cyclized with the formation of phosphiranes. It is well known that
bis(alkylidene)phosphoranes are stable only in cases when they are sterically stabilized by bulky
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substituents (tert-butyl, trimethylsilyl or 2,4,6-tri-tert-butylphenyl groups).7,8,12 In this case,
phenyl groups are not able to ensure the steric stabilization of bis(benzylidene) phosphoranes,
which easily cyclized with the formation of phosphiranes 8.
High
stereoselectivity
of
reaction
is
explained
by
formation
of
bis(alkylidene)phosphorane intermediates 9 and conrotatory mechanism of their ring-closing
reactions, according to Woodward-Hoffmann rules19 of preservation of orbital symmetry of the
co-ordinated reactions based upon conservation of orbital symmetry (Scheme 4).
Phosphiranes 8a-c are rather stable and were isolated as pure compounds, and stored in a
freezer. The phosphirane 8a bearing tert-butyl at phosphorus was purified by vacuum
distillation; phosphiranes 8b,c were purified by column chromatography. The structures of the
phosphiranes were proven by 1Н, 13С, 31Р NMR spectra and mass spectra. Chemical shifts P are
31
1
found in the very negative part of Р NMR spectra at 150 to 180 ppm. In H NMR spectra,
signals for the endocyclic CH protons are found at 3 ppm, doublets with a small constant of 2-3
13
1
Hz. In С NMR spectra at area 35-45 ppm were discovered doublets with constant JCP = ~80
Hz belonging to carbon in a three-membered cycle directly connected with the phosphorus atom.
1
The NMR spectra allow definition of the stereochemistry of phosphiranes: Н and 13С NMR
spectra show cis-position of hydrogen atoms of endocyclic СНCH-groups and their trans-
position to the substituent at phosphorus, as shown in the Scheme 3 for compounds 8a-c. The
presence of only one signal of endocyclic CH-groups (3JHH = 0 Hz) in the spectrum, and very
small constant 2JHP =1-2 Hz corresponds to trans-position of hydrogen atoms relative to the free
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electron pair at trivalent phosphorus atom. Previous studies (theoretical calculations, and
experimental, including X-Ray analysis)3,20,21 indicated that for substituents on the ring carbon
atoms, such as hydrogen or alkyl, a large coupling constant (JPH or JPC) will be observed if the
substituents (hydrogens) are cis to the lone pair at phosphorus (anti to the P-R substituent). If the
hydrogen atoms of CH-groups are anti to the lone pair (cis to the P-R substituent), the coupling
constant will be very small or not observable (Scheme 5).
Spectroscopic characteristics of phosphiranes and first of all an extremely high negative
31
1
13
field P NMR shift; high field shifts of the H and C resonances of endocyclic СН groups in
1Н and 13C NMR spectra are typical for three-membered cyclic compounds and can be explained
by the large HOMO/LUMO gap and the high p character of the phosphorus lone pair.3 The
reaction theoretically can yield several stereomers of phosphiranes 8: first of all anti-cis(meso)
8c and syn-cis(meso) 8c stereomers, and pair of trans-(+)- and trans-()-enantiomers of 2,3-
diphenylphosphiranes. However we have registered only one anti-cis-diasteremers 8a-c. No
trans-isomer was detected by 31P NMR in the reaction mixture, therefore the stereoselectivity of
reaction appears to be very high. The anti-cis-stereochemistry of phosphiranes 8a-c was
established on the basis of coupling constants of the ring protons in NMR spectra and of
comparison of NMR spectra of phosphiranes and analogous aziridines 10,11. For example, the
NMR spectra of phosphirane 8c revealed the signal of endocyclic CH-protons at 2.88 ppm,
2
3
doublet with JPH =2.0 Hz and JHH 0 Hz that is similar to those of cis-aziridine 10: H (CH)
3.89, s (i.e. 3JHH = 0 Hz). At the same time the trans-aziridine 11 reveals the signals of endocyclic
CH-protons at 3.38 and 3.66 ppm, doublets with 3JHH =14 Hz (Scheme 6).22,23
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CONCLUSION
In summary, we have developed simple stereoselective method for the synthesis of three-
membered phosphoric heterocycles – phosphiranes, which are interesting as ligands in transition
metal complexes. Researches in this direction we will develop in subsequent publications.
EXPERIMENTAL
The NMR spectra were registered on a Varіan VXR-300 spectrometer at 300 (1H), 60
(13C), and 126.16 (31P) MHz relative to Me4Sі (1H, 13C) or 85% H3PO4 (31P). Solvents were
preliminarily distilled in an inert atmosphere: diethyl ether, hexane, benzene, and carbon
tetrachloride over phosphorus pentoxide, methanol and triethylamine over sodium, and ethyl
acetate over calcium chloride. Tribenzylphosphine 2c was prepared by reaction of
benzylmagnesium chloride with phosphorus trichloride using a modification of the reported
methods.16c,d Other reagents, silica gel and TLC plates (Polіgram SIL G/UV254) were purchased
from Merck (Germany), Fluka (Buchs, Switzerland), and Acros and were used without further
purification.
tert-Butyl-dibenzylphosphine 2a
To a solution of tert-butyldichlorophosphine (0.1 mol) in diethyl ether (100 mL) with
stirring and cooling to 0оС a solution of of benzylmagnesium chloride (0.22 mol) in diethyl ether
was added. The reaction mixture was stirred for 1 h at room temperature, then refluxed for 2 h.
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After the mixture was filtered, the solvent was removed under reduced pressure, and the residue
was extracted with hot hexane. The extract was evaporated and the residue was distilled in
1
vacuum. Yield 60%, bp 130-140оС (0.1 mmHg). H NMR (CDCl3): 1.1 (d, JHP =8 Hz, 9H,
CH3), 2.9 (d, JHP =4 Hz, 4H, CH2Ph), 7.1-7.5 (m, 10H, Ph). 31P NMR (CDCl3):  11.0 ppm.
Anal. Calcd. for C18H23P: C 79.97; H 8.58; P 11.46%. Found: C 79.63; H 8.55; P 11.32%.
tert-Butyl-dibenzylphosphine oxide 7a
To a solution of tert-butyl-benzylphosphine 2а (0.01 mol) in 10 mL of hexane was added
TMEDA (0.015 mol) and butyllithium (0.012 mol) in hexane solution. The reaction mixture was
31
heated for 1 h at 50°С. The course of reaction was monitored by P NMR spectra. Only one
signal P = ppm was detected in the reaction mixture to indicate that the reaction was
completed. Then the reaction mixture was cooled to 60°C and of tetrachloromethane (0.015
mol) was added. The mixture was stirred at room temperature for 0.5 hr, filtered, solvent was
evaporated under vacuum and the viscous yellow oil of P-chloroylide 5, P =73 ppm, was
obtained. The compound 5 was dissolved in 5 mL of diethyl ether and 0.015 mol of methanol
was added at 0°С. The mixture was left at room temperature for 0.5 hr. Then volatile products
were evaporated under vacuum and a yellowish crystal product was obtained in the residue.
o
1
Yield 80%. Mp 158-159°С (lit.24 mp 159-162 C]. H NMR (CDCl3):  1.04 (d, JHР =14.4 Hz,
9Н, CH3C); 3.01 (dq, JHР =15 Hz, J =12 Hz, 4Н, РСН2); 7.21 (m, 10Н, С6H5). 31P NMR
(CDCl3): P 53 ppm.
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Tribenzylphosphine oxide 7c
25
The reaction was carried out analogously to 7a. Yield 65%. Mp 215°C (lit. 210-
1
31
212oC). H NMR (CDCI,):  2.95 (d, JHP = 13 Hz, CH2, 6H); 7.05 (m, C6H5, 15H). P NMR
(CDCl3): P 41.0 ppm.
Anti-Cis 1-tert-Butyl-2,З-diphenylphosphirane 8а
To a solution of of tert-butyl-dibenzylphosphine 2а (0.01 mol) in hexane (10 mL) was
added ТМЕDА (0.025 mol) and butyllithium (0.025 mol) in hexane solution. The reaction
mixture was heated for 3 h at 50 °С. The course of reaction was monitored by 31Р NMR
spectroscopy. When the reaction was completed, in a spectrum of red colored solution was found
only one signal, P 25.5 ppm, belonging to dilithium tert-butyl-dibenzylphosphine 4a.
To the reaction solution was added of tetrachloromethane (0.03 mol) at 60°C. The color of the
reaction solution changed from red to yellow. A precipitate of lithium chloride was filtered off,
the solvent was evaporated and the residue was distilled in vacuum.
1
Yield 50%. Bp 130 °С (0.05 mmHg). Mp 46-47°С (lit.16a). H NMR (CDCl3):  1.18 (d, JHP
13
=12.6 Hz, 9Н, СН3С); 3.13 (d, JHP =2.5 Hz, 2Н, РСН), 7.05-7.45 (m, 10Н, С6Н5). C NMR
(CDCl3):  16.0; 17.8; 33.5; 38.6; 35,7; 125.9; 128.0; 130.2; 130.3; 137.0; 137.1 (C6H5). 31Р
NMR (CDCl3): Р 151 ppm, m/e (70 eV): 268 (M+). Anal. Calcd. for С18Н21Р.: C 80.57; H
7.89; Р 11.54%. Found: C 80.57; H 7.89; Р 11.65%.
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N,N-Diethylaminodibenzylphosphine 2b
l-Diethylamino-2,3-diphenylphosphirane was prepared using a modification of the
reported method.16c To a solution of diethylaminodichlorophosphine (0.1 mol) in diethyl ether
(100 mL) was added a solution of benzylmagnesium chloride (0.22 mol) in the same solvent with
о
stirring and cooling to 0 С. The reaction mixture was stirred for 1 hr at room temperature, then
refluxed for 2 hr. The reaction mixture was filtered off, the solvent was evaporated, and the
residue was extracted with hot hexane. Then the solvent was evaporated, a residue was distilled
in vacuum. Yield 60%, bp 145 оС (0.1 mmHg).
Spectroscopic data of 2b were not described in the previous reference.16c 1H NMR (CDCl3): 
31
0.95 (t, J =7 Hz, 6H, CH3); 2.9 (m, 4H, CH2Ph); 3.1 (m, 4H, NCH2); 7.1-7.5 (m, 10H, Ph). P
NMR (CDCl3): P 66 ppm.
Anti-Cis l-Diethylamino-2,3-diphenylphosphirane 8b
To a solution of diethylaminodibenzylaminophosphine 2b (0.01 mol) in hexane (10 mL)
at 25oC was added ТМЕDА (0.025 mol) and butyllithium (0.022 mol) in hexane. The reaction
mixture was stirred for 0.5 h at room temperature, and refluxed for 3 hr at +50 °С. Then to a
reaction solution at 60 oC was added tetrachloromethane (0.025 mol). The reaction mixture was
stirred for 1 h at room temperature, filtered, and the solvent was evaporated. The residue was
purified by column chromatography with deoxygenated silica gel (toluene-hexane as eluent).
Yield of 35%. Yellow oil.
1H NMR (C6H6):  0,93 (t, JHH = 7.0 Hz, 6H, CH3); 2.8 (m, 4H, NCH2); 3.9 (d, JPH ~1 Hz, 2H,
13
PCH); 7.0 (m, 10H, H-Ar). C NMR (C6H6): 16.0; 39.0, d (J 44.3, PCH); 45,6; 45.8; 125.9;
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128.0; 130.2; 130.3; 137.0; 137.1 (Ph). 31Р NMR (C6D6): P = 95 ppm. m/e: (70 eVВ): 283
(M+). Anal. Calcd. for C18H22NP: N 4.94; P 10.93%. Found: N 4.91; P 11.05%.
Anti-Cis-1-Benzyl-2,3-diphenylphosphirane 8c
o
To a solution of tribenzylphosphine (0.02 mol) in hexane (10 mL) at cooling to 20 C
was added TMEDA (0.02 mol) and butyllithium (0.02 mol) in hexane. The reaction mixture was
heated for 3 h at +50°С. The course of reaction was monitored by means of 31Р NMR
spectroscopy. When the reaction was completed in a spectrum was found only signal P= 51.1
ppm, belonging to the benzyl-bis(lithiumbenzyl)phosphine 4c.
To a solution of dilithium derivative 4c at 60°C was added tetrachloromethane (0.025 mol). The
temperature of reaction mixture was raised to room, the reaction mixture was evaporated under
vacuum. The product was isolated by column chromatography with deoxygenated silica gel,
using toluene-hexane as eluent. The crystalline product was additionally recrystallized from
hexane. Yield 25%, mp 80°C.
1H NMR (CDCl3):  2,33 (d, JPH =5 Hz, PCH2); 2.88 (d, JPH =2.0 Hz, 2H, PCH); 6.5-7,8 (m,
13
15Н, Ph). C NMR (C6H6): 35,9 (d, JPC =36 Hz, PCH2); 36.5 (d, JPC =38 Hz, PCH); 123.6;
123.7; 125.5; 125.7; 126.9; 128.0; 130.8; 130.9; 137.2; 137.6 (Ph). 31Р NMR (CDCl3): P = 180
ppm. m/e (70 eV): 302 (M+). Anal. Calcd. for C21H19P: C 84.0; H 6.58; P 10.29%. Found: C
83.42; H 6.33; P 10.24%.
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