A convenient approach to N-(Di-tert-butylphosphanyl)- and N-(Di-tert-butylphosphoroselenoyl)formamidinium Salts: Carbene precursors

Article abstract of DOI:10.1002/ejic.201301365

The reactions of (di-tert-butylphosphanyl)amines and P,P-di-tert- butylphosphinoselenoic amides with Alder's dimer were studied. For di-tert-butylphosphanylamines, the reaction proceeds by primary electrophilic attack of Alder's dimer at the phosphorus atom to afford a dicationic salt 3. The deprotonation of 3 led to N-phosphanylformamidine 5 ( phosfam ). Alkyl(di-tert-butylphosphanyl)amines reacted with Alder's dimer in a 2:1 molar ratio to give N-phosphanylformamidinium salts; the second equivalent of (alkylamino)phosphane acts as a base. (Arylamino)phosphanes reacted with Alder's dimer to give benzazaphospholium derivatives. To direct the electrophilic attack of Alder's dimer at the nitrogen atom, phosphinoselenoic amides were used. They reacted with Alder's dimer at the selenium atom followed by a selenium-phosphorus shift to give N-(di-tert-butylphosphoroselenoyl) formamidinium salts. The phosphinoselenoic amides with bulky substituents (adamantyl, tBu) underwent cleavage of the N-alkyl bond to afford phosfams. Various key intermediates such as 3 and 22b were isolated and characterized. A convenient method for the synthesis of carbene precursor P^III and P^V N-substituted formamidinium salts was developed. Carbene precursor P^III and P^V N-substituted formamidinium salts are obtained by the reaction of (di-tert-butylphosphanyl)amines and P,P-di-tert-butylphosphinoselenoic amides with Alder's dimer. The primary electrophilic attack of Alder's dimer proceeds at the phosphorus atom of the phosphanylamines or at the selenium atom of the phosphinoselenoic amides. Copyright

Full text of DOI:10.1002/ejic.201301365

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DOI:10.1002/ejic.201301365
A Convenient Approach to N-(Di-tert-butylphosphanyl)-
and N-(Di-tert-butylphosphoroselenoyl)formamidinium
Salts: Carbene Precursors
Anatoliy Marchenko,[a] Georgyi Koidan,[a] Anastasiya Hurieva,[a]
Aleksandr Savateev,[a] Alexander B. Rozhenko,[a]
Jean-Marc Sotiropoulos,[b] Svitlana V. Shishkina,[c]
Oleg V. Shishkin,[c,d] and Aleksandr Kostyuk*[a]
Keywords: Carbene precursors / Phosphorus heterocycles / Selenium / DFT calculations
The reactions of (di-tert-butylphosphanyl)amines and P,P-di-
tert-butylphosphinoselenoic amides with Alder’s dimer were
studied. For di-tert-butylphosphanylamines, the reaction
proceeds by primary electrophilic attack of Alder’s dimer at
rect the electrophilic attack of Alder’s dimer at the nitrogen
atom, phosphinoselenoic amides were used. They reacted
with Alder’s dimer at the selenium atom followed by a selen-
ium–phosphorus shift to give N-(di-tert-butylphosphoro-
the phosphorus atom to afford a dicationic salt 3. The depro- selenoyl)formamidinium salts. The phosphinoselenoic
tonation of 3 led to N-phosphanylformamidine 5 (“phos-
fam”). Alkyl(di-tert-butylphosphanyl)amines reacted with
Alder’s dimer in a 2:1 molar ratio to give N-phosphanylform-
amidinium salts; the second equivalent of (alkylamino)phos-
phane acts as a base. (Arylamino)phosphanes reacted with
Alder’s dimer to give benzazaphospholium derivatives. To di-
amides with bulky substituents (adamantyl, tBu) underwent
cleavage of the N–alkyl bond to afford phosfams. Various key
intermediates such as 3 and 22b were isolated and charac-
terized. A convenient method for the synthesis of carbene
precursor PIII and PV N-substituted formamidinium salts was
developed.
phane in tetrahydrofuran (THF) in the presence of sodium
triflate. The NHCP ligands were employed in the synthesis
of transition metal complexes either from their silver com-
plexes[3] or directly by reactions with metal salts.[4] These
complexes have shown promising activity in nitrene transfer
reactions.[3] The stability of NHCP ligands A (Figure 1) is
significantly dependent on the bulkiness of the substituents
at the phosphorus atom, and the di-tert-butylphosphanyl
group provides the most stable ligands.
Introduction
Among the available approaches to carbenes, the most
common synthetic route is the deprotonation of cationic
heterocycles or acyclic iminium salts. Their design and syn-
thesis constitute the main challenge, as the method works
quite well. Recent reviews focus on their synthesis and the
subsequent carbene preparation.[1]
Recently, it has been shown that N-phosphanyl-substi-
tuted N-heterocyclic carbenes (NHCP ligands) derived
from imidazole, benzimidazole, and triazole can be isolated
as discrete compounds.[2] The main approach to NHCP li-
gands is based on the deprotonation of N-(di-tert-butyl-
phosphanyl)azolium triflates. These salts were prepared by
treating N-substituted azoles with bromodi-tert-butylphos-
Figure 1. Available NHCP ligands and N-phosphanylformamidin-
ium salts.
[a] Institute of Organic Chemistry, National Academy of Sciences
of Ukraine,
Murmanska 5, 02660 Kyiv 94, Ukraine
www.ioch.kiev.ua
Continuing our research on the synthesis of analogous
acyclic N-phosphanyl carbenes, we applied the well-devel-
oped method for the synthesis of N-phosphanylazolium tri-
flates to N,N-dialkyl-NЈ-aryl(alkyl)formamidines. New N-
phosphanylformamidinium salts of type B were synthesized
by the reaction of N,N-dialkyl-NЈ-aryl(alkyl)formamidines
with bromodiphenylphosphane in tetrahydrofuran in the
presence of sodium triflate (Figure 1).[5] It should be noted
that N,N-dialkyl-NЈ-aryl(alkyl)formamidines do not react
[b] CNRS/Univ. de Pau & des Pays de l’Adour, IPREM, UMR
5254,
2 Avenue du Président P. Angot, 64053 Pau cedex 09, France
[c] SSI “Institute for Single Crystals”, National Academy of
Sciences of Ukraine,
Lenin ave. 60, 61001 Kharkiv 01, Ukraine
[d] Department of Inorganic Chemistry, V. N. Karazin Kharkiv
National University,
4 Svobody sq., Kharkiv 61202, Ukraine
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201301365.
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with the more bulky bromodi-tert-butylphosphane under
the same conditions. The deprotonation of these salts B
gave C-phosphanylformamidines via intermediate carbenes
that were identified spectroscopically and trapped by reac-
tion with selenium. The failure to prepare stable carbenes
indicates that more kinetic stabilization is required to pro-
vide stability to carbenes of this type. Therefore, other ap-
proaches to N-phosphanylformamidinium salts bearing
bulky groups at the phosphorus atom should be developed.
Alder and co-workers[6a,6b] have introduced into synthetic
practice new powerful reagents 1 (Alder’s dimer) that can
be readily prepared by the reaction of N,N-dialkylform-
amides with triflic anhydride. They react more cleanly and
in higher yields compared to Vilsmeier–Haack conge-
ners.[6c]
Scheme 2. Reaction of aminophosphane 2 with 1b.
Compound 3 is a moisture-sensitive, colorless, crystalline
substance. The structure of 3 was proved by H and 13C
1
NMR spectroscopy and X-ray diffraction analysis (Fig-
ure 2).
Alder’s dimer reacts readily with primary and secondary
amines to give trialkyl- or tetraalkylformamidinium salts C,
respectively (Scheme 1). The first stable acyclic diami-
nocarbene D (R = iPr) was prepared in 1996 by Alder by
this approach.[7] Bertrand et al. utilized it in the reaction
with phosphanes for the preparation of the carbene precur-
sors E and carbenes F.[8]
Figure 2. Molecular structure of 3 according to the X-ray diffrac-
tion data. Here and in the following structure representations, the
thermal ellipsoids of atoms are shown at 50% probability levels.
Some hydrogen atoms are omitted for clarity.
The N1 atom forms two N–C(iPr) single bonds and the
C1–N1 bond, the length of which [1.277(3) Å] is even
shorter than the mean value for C(sp2)=N(3) double bonds
(1.316 Å).[10] The tetracoordinated phosphorus atom forms
three P1–C single bonds and one P1=N2 double bond [the
length of 1.606(2) Å is close to the mean value (1.599 Å)
for P=N double bonds]. Quantum chemical calculations
(RIJCOSX-B3LYP-D3/TZVP) yield a similar structure for
the dicationic part of 3 [d(C=N) = 1.276 Å, d(C–P) =
1.870 Å, Є(PCN) = 134.2°]. The natural population analy-
sis (NPA) at the B3LYP/TZVP level of theory predicted the
double bond of the C=N(iPr)2 moiety (calculated Wiberg
bond order 1.78) but a slightly negative total charge on the
nitrogen atom (–0.19 e) and delocalization of only +0.52 e
on the N(iPr)2 fragment.
Scheme 1. Reactions of Alder’s dimer with amines and phosphanes.
The data presented above allowed us to suppose that ac-
cess to the previously unknown N-phosphanylformamidin-
ium and N-(phosphoroselenoyl)formamidinium salts G, the
precursors for the corresponding carbenes, would be pro-
vided by the (dialkylamino)methylation of aminodi(tert-
butyl)phosphanes
amides.
or
di-tert-butylphosphoroselenoyl
Results and Discussion
Compounds of type E can be deprotonated with 1 equiv.
of lithium bis(trimethylsilyl)amide to give stable carbenes of
phosphonium type F (Scheme 1) as shown by Bertrand.[8]
If salt 3 is deprotonated with 2 equiv. of base, N-phosphan-
1. Reactions of Alder’s Dimer with Aminophosphanes
1.1 Aminodi(tert-butyl)phosphane
Amino(diorganyl)phosphanes are labile compounds ylformamidine 5 is formed (Scheme 3). This type of hardly
prone to dimerization under elimination of ammonia.[9] accessible compounds (named “phosfams”) was recently
These species can be stabilized by the introduction of bulky prepared by the reaction of iPr2NCN with chlorophos-
substituents at the phosphorus atom. For instance, amino- phanes R2PCl (R = iPr2N, Ph, Et, iPr) in the presence of
di(tert-butyl)phosphane (2) is quite a stable compound. 1 equiv. of hydridozirconocene.[11] Phosfam 5 is an air-sensi-
Similarly to Ph3P, aminophosphane 2 was found to react tive, colorless, crystalline compound. It possesses a trans
1
readily with Alder’s dimer 1b in a 1:1 molar ratio to afford configuration, as evidenced by its H and 13C NMR spec-
the dicationic salt 3 (Scheme 2). The 31P NMR spectrum of tra, which are similar to those of the previously described
the reaction mixture exhibited one singlet at δ = 66 ppm.
iPr analogue.[11]
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(Scheme 5). Our approach to direct alkylation at the sp2
nitrogen atom by oxidation of phosfam 5 with selenium
failed, as 8 was alkylated at the selenium atom to afford salt
1
10, which exhibited a coupling constant of JP,Se = 480 Hz,
typical for a single P–Se bond, in the 31P NMR spec-
trum.[13]
At the same time, the protonation of 8 with triflic acid
proceeded at the imine nitrogen atom to give 11. This was
confirmed by a coupling constant (1JP,Se = 800 Hz) typical
for a P=Se double bond and by the doublet of doublets for
Scheme 3. Synthesis of phosfam 5.
3
1
the CH proton (3JP,H = 13.2 Hz, JH,H = 9.6 Hz) in the H
NMR spectrum.
The formation of phosfam 5 can be rationalized by the
nucleophilic attack of the carbocationic center by the nitro-
gen atom of the iminophosphane I formed upon deproton-
ation of salt 3 (Scheme 3). Further deprotonation of the
phosphoniaaziridine II led to the cleavage of the P–C bond
to afford phosfam 5. Our attempts to identify these inter-
mediates failed. When phosfam 5 itself (1 equiv.) was used
for the deprotonation of salt 3, the 31P NMR spectra of the
reaction mixture exhibited a doublet for 6 at δP = 63 ppm
(JP,H = 445 Hz) and a singlet at δP = 51 ppm. The latter
transformed completely into the doublet of 6 at room tem-
perature in 15 h (Scheme 4).
1.2 (Alkylamino)di(tert-butyl)phosphanes
As the N-phosphanylformamidines cannot serve as start-
ing materials for the synthesis of the target salts, we deemed
it appropriate to investigate the reaction of Alder’s dimer
with phosphanes bearing a secondary amine group at the
phosphorus atom.
(Alkylamino)di(tert-butyl)phosphanes 12 reacted with
Alder’s dimer in a 2:1 molar ratio, and the second equiva-
lent of aminophosphane acted as a base (Scheme 6). The
mechanism for the formation of 13 is probably the same
as that for the formation of phosfam 5, in which primary
electrophilic attack of Alder’s dimer at the phosphorus
atom affords an intermediate of type 3. The intermediate is
further deprotonated by a second molecule of aminophos-
phane to give compounds 13, which are white, moisture-
sensitive solids. The H and 13C NMR spectra are consis-
1
tent with the proposed structures. The structures of 13a and
13b were confirmed by X-ray diffraction analyses (Fig-
ure 3). The positive charges in both compounds are par-
tially located at the N1 atom, which forms two single N–
C(iPr) bonds and one double bond [C1=N1 1.307(1) Å in
13a and 1.308(3) Å in 13b] similar to that in 3. In 13a, the
positive charge is delocalized on the N(iPr)2 group
(+0.22 e), the central CH fragment (+0.57 e), and
N(Me)[P(tBu)2] (the remainder). This is in line with the par-
tially double-bond character of the two N1–C(H)–N2(iPr)2
bonds (the calculated Wiberg bond indices are 1.39 and
1.42 for the C–N1 and C–N2 bonds, respectively), which
correspond to the longer calculated C–N2 bond than that
in 3.
Scheme 4. Deprotonation of salt 3 with phosfam 5.
Therefore, the signal at δP = 51 ppm can be assigned to
phosphoniaaziridine II. This is in line with the stepwise na-
ture of the formation of phosfam 5 from salt 3.
Although N-alkyl(aryl)formamidines are alkylated at the
sp2 nitrogen atom to afford formamidinium salts, which are
carbene precursors,[12] N-phosphanylformamidines are alk-
ylated only at the phosphorus atom.[11] Even the presence
of bulky tert-butyl groups at the phosphorus atom does not
change the course of the reaction, and 5 was also alkylated
at the phosphorus atom to afford the phosphonium salt 7
Scheme 6. Reaction of (alkylamino)phosphanes 12 with Alder’s di-
mer 1b.
Notably, the 31P NMR spectrum for 13a has three broad-
ened peaks, whereas two signals are observed in the spec-
trum of 13b at room temperature. At 80 °C, coalescence oc-
curred (Figure 4) to give one broad peak at δ ≈ 138 ppm.
On cooling, identical spectra were observed.
Scheme 5. Attempts to prepare N-phosphanylformamidinium salts
from phosfam 5.
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Figure 5. Possible equilibrium responsible for the multiple signals
in the 31P NMR spectra of 13.
details). Therefore, an equilibrium between 13-I and 13-II
(13-III) and even between 13-II and 13-III seems to be un-
likely. At the same time, calculations predict a very close
thermodynamic stability (ΔG within 1.3 kcal/mol) for three
conformations of 13 (Figure 6; 13aA, 13aB, and 13aC).
Thus, the three different signals at room temperature in the
experimental 31P NMR spectra (Figure 4) can be attributed
to the simultaneous existence of the three above-mentioned
rotamers in solution. The process probably corresponds to
the exchange between three conformations 13aA–13aC by
a hindered rotation about the N–P and (P)N–C bonds. The
Figure 3. Molecular structures of 13a and 13b according to the X-
ray diffraction data.
Initially, we assumed that the three signals in the 31P
NMR spectrum for 13a resulted from its equilibrium with
two linear forms 13-I and 13-III via the phosphoniaazirid-
ine intermediates 13-II (Figure 5).
Quantum chemical (DFT) calculations for a set of com-
pounds 13a–13c [R = Me (13a), iPr (13b), and mesityl
(Mes; 13c)] indicated that for these three derivatives, the
isomer I is the most stable one, followed by III and II. The
differences in energy between I and II and between I and
III are particularly large in the case of 13a (70.6 and
59.5 kcal/mol, respectively). For 13b and 13c, these differ-
Figure 6. Jmol plots of equilibrium structures and relative energies
ences are 21–33 kcal/mol (see Supporting Information for (RIJCOSX-B3LYP-D3/TZVP) for different conformations of 13a.
Figure 4. 31P NMR spectra of 13a from –20 (bottom) to 80 °C (top).
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latter clearly possesses a partially double-bond character phosphane 15 to afford intermediate IV (Scheme 8). The
(Figure 6). In contrast, structure 13aD is definitely less fa- latter cyclized by a carbocationic mechanism similar to that
vorable and should be excluded from consideration.
for N-aryl(pyrazolyl)phosphinimidic isocyanates.[14]
1.3 (Arylamino)di(tert-butyl)phosphanes
Like (alkylamino)phosphanes 12, (arylamino)phos-
phanes 15 reacted with Alder’s dimer 1a in a 2:1 molar ratio
but afforded cyclic compounds 16 and triflic salts 17
(Scheme 7).
Scheme 8. Possible intermediates in the formation of 16.
2. Reactions of Phosphinoselenoic Amides with Alder’s
Dimer
Scheme 7. Reaction of (arylamino)phosphanes 15 with Alder’s di-
mer 1a.
2.1 N-Arylphosphinoselenoic Amides
As the reactions of Alder’s dimer with aminophosphanes
2, 12, and 15 proceed at the phosphorus atom, one might
expect that its protection would change the direction of the
reaction towards the amino group. Indeed, 18a–c reacted
readily with Alder’s dimer 1b in a 1:1 molar ratio to give
salts 19a–c and the triflic salt of formamide 4 (Scheme 9).
The latter is sparsely soluble in diethyl ether, allowing its
complete separation from salts 19. Alternatively, after re-
moval of the solvent, the residue can be treated with water
to remove the triflic salt of formamide 4.
Compounds 16 are air-stable crystalline solids. The struc-
ture of 16a was elucidated by 1H and 13C NMR spec-
troscopy and X-ray diffraction analysis (Figure 7). Analysis
of the bond lengths in both molecules of 16a (16a-A and
16a-B) located in the asymmetric part of the crystal unit
cell demonstrates that the phosphorus atom forms four sin-
gle bonds (three P–C bonds and one P–N bond). In con-
trast to 3, 13a, and 13b, the lengths of the P–N bonds in
16a-A and 16a-B [1.654(5) and 1.658(4) Å, respectively]
correspond to the mean value of the P(4)–N(3) single bond
(1.662 Å). Therefore, it can be assumed that the positive
charge in cation 16a is localized at the phosphorus atom.
Scheme 9. Reaction of phosphinoselenoic amides 18 with Alder’s
dimer 1b.
Salts 19 are colorless, crystalline, air-stable compounds,
which were unambiguously characterized by elemental
analyses and spectroscopic methods and additionally by X-
ray diffraction analysis for 19a (Figure 8). They were readily
reduced with (Me2N)3P to give the previously unknown
salts 20a–c (Scheme 10). According to the X-ray diffraction
data, the N1 atom forms two N–C(iPr) single bonds and
one shortened C1–N1 bond [1.305(2) Å] in 19a and 20a. In
both cases, similar charge distributions were found. In 19a
and 20a, the most positive charge is localized on the central
CH moieties (+0.59 e in both cases), and much less is con-
centrated on the N(iPr)2 group (+0.25 and +0.23 e, respec-
tively). Again, the N1–C(H) and C(H)–N2(iPr)2 bonds are
shortened (1.338 and 1.307 Å, respectively, in 19a and 1.334
and 1.312 Å, respectively, in 20a) and have partially double-
Figure 7. Molecular structure of 16a according to X-ray diffraction
data.
Similarly to other aminophosphanes, the formation of 16 bond character [calculated bond orders for 19a: 1.32 (1.36
probably proceeded by generation of dicationic salt III, in 20a) and 1.46 (1.44 in 20a) for the N1–C(H) and C(H)–
which was deprotonated with a second equivalent of amino- N2 bonds, respectively].
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Scheme 11. Reaction of phosphinoselenoic amides 21 with Alder’s
dimer 1b.
(Ad)] are irreversible and were complete at 25 °C after 3 h
to give triflate salt 11 and probably salts 24c and 24d, as an
alkaline hydrolysis of 24d after separation of 11 gave
AdOH. In contrast, the reactions of 21a and 21b (Me, iPr)
led to salts 23a and 23b, but the reaction proceeded very
slowly; 30 min after the reactants were mixed, the 31P NMR
spectra exhibited weak signals of the salts 23a and 23b, the
starting compounds 21a and 21b, and strong signals of in-
termediates at δP = 112 (22a) and 106 ppm (22b) with JP,Se
350–380 Hz, typical for P–Se single bonds. Eventually, the
intensity of the signals of 23a and 23b increased, and the
intensity of the other signals decreased. The final spectral
yields of the salts reached 89% in 30 h for 23a and 71% in
72 h for 23b. Therefore, we could conclude that Alder’s di-
mer reacted with phosphinoselenoic amides 18 and 21 at
the selenium atom to afford the dicationic salts of type 22
and diisopropylformamide 4. The latter deprotonated salt
22 to initiate a [1,3] shift of the aminomethylene group from
the selenium atom to the nitrogen atom. We successfully
isolated the intermediate 22b. It is a transparent, crystalline,
moisture-sensitive solid. The structures of intermediate 22b
and compound 23b were confirmed by X-ray diffraction
analyses (Figure 9). Analysis of the bond lengths in inter-
mediate 22b indicates that both nitrogen atoms form two
single bonds [two N–C(iPr) bonds for the N1 atom and N–
C(iPr) and N–H bond for the N2 atom] and short N1=C1
[1.275(6) Å] and N2=P1 bonds [1.616(3) Å]. Despite the
very short calculated C=N(iPr)2 bond length (1.283 Å), one
of the two positive charges in 22 is only partly located on
the N(iPr)2 moiety (+0.42 e) and, hence, the proposed
mesomeric form with the positively charged nitrogen atom
is not fully correct (the total charge on N2 is –0.26). The
almost full positive charge unit (+0.85) is delocalized within
the SeC(H)N2(iPr)2 fragment. The calculated Wiberg bond
Figure 8. Molecular structures of 19a and 20a according to the X-
ray diffraction data. The triflate anions are omitted for clarity.
Scheme 10. Reduction of salts 19.
Compounds 20a–c are colorless, moisture-sensitive, crys-
talline compounds, the structures of which were confirmed
1
by H and 13C NMR spectroscopy.
2.2 N-Alkylphosphinoselenoic Amides
To extend our method for the synthesis of salts 19, we indices for the C–N and Se–C bonds (1.64 and 1.17, respec-
investigated the reaction of Alder’s dimer with N-alkyl-sub- tively) also indicate participation of the nitrogen and selen-
stituted phosphinoselenoic amides 21a–d (Scheme 11).
The N-alkylphosphinoselenoic amides 21 reacted more positive charge is concentrated on the phosphorus atom.
slowly than the N-aryl derivatives 18, probably because of In contrast to 13 and 19, in 23, the calculated bond
ium atoms in the positive charge delocalization. The second
the lower acidity of the amide hydrogen atom. Moreover, lengths and Wiberg bond indices for C–N1 and C–N2 in
the rate and composition of the products of the reaction the N1–C(H)–N2(iPr)2 moiety differ significantly (1.296
depended dramatically on the bulkiness of the alkyl substit- and 1.405 Å, 1.53 and 1.05, respectively). The P1 environ-
uent. Thus, the reactions of 21c and 21d [tBu, adamantyl ment is almost orthogonal to the CH–N2 π-system. The
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to afford phosfams. The developed method makes the carb-
ene precursor formamidinium salts bearing either a tri- or
pentavalent phosphorus group at the nitrogen atom readily
available. Deprotonation of the formamidinium salts is un-
der investigation and will be reported separately.
Experimental Section
General: All procedures with air- and moisture-sensitive com-
pounds were performed under dry argon in flame-dried glassware.
Solvents were purified and dried by standard methods. Melting
points were determined with an electrothermal capillary melting
point apparatus. 1H NMR spectra were recorded with a Bruker
Avance DRX 500 (500.13 MHz) or
a
Varian VXR-300
(299.94 MHz) spectrometer. 13C NMR spectra were recorded with
a Bruker Avance DRX 500 (125.75 MHz) spectrometer. 31P NMR
spectra were recorded with a Varian VXR-300 (121.42 MHz) or a
Bruker Avance 400 spectrometer (161.98 MHz). Chemical shifts (δ)
are reported in ppm downfield relative to internal tetramethylsilane
(TMS) for 1H and 13C and external 85% H3PO4 for 31P.
Chromatography was performed on Gerudan SI60 silica gel. Ele-
mental analyses were performed at the analytical laboratory of the
Institute of Organic Chemistry, National Academy of Sciences of
Ukraine.
Figure 9. Molecular structures of 22b and 23b according to the X-
Calculations: All structures were optimized by using Gaussian 09[15]
(see Supporting Information) and the ORCA program package
(version 2.9).[16] The B3LYP[17,18] hybrid functional including the
last version of Grimme’s correction for dispersion interactions
(B3LYP-D3)[19] and TZVP basis sets (the TZV basis sets of triple-
zeta quality[20] plus one p function set for hydrogen atoms or one
d function set for all other atoms). For more efficient calculations,
the parallel RIJCOSX algorithm[21,22] was used with the accurate
grid parameters (Grid5, GridX6). The vibrational frequencies were
calculated numerically, and no imaginary frequencies were found
for the equilibrium geometries. The relative energies (ΔG) were cal-
culated by using total energy values corrected for Gibbs free energy;
no scaling was used. The NPA charges and Wiberg indices[23] were
calculated by using the natural bond orbital (NBO) procedure (ver-
sion 3.1) implemented in the Gaussian 09 set of programs. The
structures were presented graphically by using the Jmol program.[24]
ray diffraction data. Triflate anions are omitted for clarity.
positive charge (+0.91 e) is delocalized in the C(H)–N2-
(iPr)2 moiety, and its largest part is concentrated on the
central carbon atom. Thus, the structure of 23 is best repre-
sented by the Lewis structure with the positive charge at
the carbon atom.
Conclusions
We have developed a convenient approach to N-phos-
phanyl- and N-(phosphoroselenoyl)formamidinium salts
from the reactions of aminophosphanes or phosphinosele-
noic amides with Alder’s dimer. For the aminophosphanes,
the primary electrophilic attack of Alder’s dimer proceeded
at the phosphorus atom. The subsequent reaction course
depended on the substituents at the nitrogen atom. The
aminophosphane bearing an NH2 group gave the amino-
phosphonium salt 3, which, upon treatment with a base,
rearranged into neutral phosfam 5. The aminophosphanes
bearing an NHAlkyl group reacted with Alder’s dimer in a
2:1 molar ratio. The reaction proceeded at the phosphorus
atom, and the second equivalent of aminophosphane acted
as a base to induce the rearrangement to the final N-phos-
phanylformamidinium salt. The aminophosphane bearing
an NHPh group also reacted at the phosphorus atom fol-
lowed by cyclization to form benzazaphospholium deriva-
tives. Phosphinoselenoic amides reacted with Alder’s dimer
at the selenium atom. Depending on the substituents at the
nitrogen atom, these intermediates behaved differently. N-
Aryl- and N-alkyl- (Me, iPr) -phosphinoselenoic amides
readily gave formamidinium salts, and the latter reacted
more slowly. The phosphinoselenoic amides with bulky sub-
Single-Crystal X-ray Diffraction Analysis: X-ray diffraction analy-
ses were performed with automatic Bruker APEX II (3, 13a, 13b,
16, 20a, 22b, and 23b) and Xcalibur 3 (19a) diffractometers (graph-
ite-monochromated Mo-Kα radiation, CCD detector, ω-scanning).
The structures were solved by direct methods by using the
SHELXTL package.[25] The positions of the hydrogen atoms were
located from electron-density difference maps and refined in iso-
tropic approximations, except for 16, for which the hydrogen atoms
were refined by a “riding” model with Uiso = nUeq of the carrier
atom (n = 1.5 for methyl groups and n = 1.2 for other hydrogen
atoms). The crystallographic data and experimental parameters are
listed in Table S1. CCDC-928575 (for 3), -959126 (for 13a), -959127
(for 13b), -928576 (for 16), -959128 (for 19a), -959129 (for 20a),
-959130 (for 22b), and -959131 (for 23b) contain the crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Diisopropyl[amino(di-tert-butyl)phosphonio]methyleneammonium
Bis(trifluoromethanesulfonate) (3): To a suspension of 1b (0.01 mol)
in dichloromethane (DCM; 30 mL) cooled to –10 °C was added a
stituents (Ad, tBu) underwent cleavage of the N–alkyl bond solution of 2 (0.01 mol) in DCM (30 mL) with stirring. A solid
Eur. J. Inorg. Chem. 2014, 1192–1203
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precipitated over 5 min. The reaction mixture was stirred at 20 °C
for 1 h. The precipitate was collected by filtration, washed twice
with DCM, and dried in vacuo to give a white solid (5.54 g, 97%);
finely ground selenium (2.7 mmol) at 20 °C, and the reaction mix-
ture was stirred for 15 min. The unreacted selenium was removed
by filtration, and the benzene was evaporated. The residue was
m.p. 160–162 °C (CH3CN). 31P NMR (CD3CN): δ = 66.2 ppm. 1H recrystallized from pentane. Yield 0.82 g (94%); m.p. 105–106 °C.
NMR (CD3CN): δ = 1.57 (d, JP,H = 18.3 Hz, 18 H, CH3), 1.63 (d,
31P NMR (CDCl3): δ = 99.4 (JP, Se = 665 Hz) ppm. 1H NMR
JH,H = 6.6 Hz, 12 H, CH3), 4.86 (m, 1 H), 5.56 (m, 1 H), 5.93 (d, (CDCl3): δ = 1.25 (d, JP,H = 6.8 Hz, 6 H, CH3), 1.26 (d, JP,H
=
JP,H = 6 Hz, 2 H, NH2), 9.1 (d, JP,H = 30 Hz, 1 H, CH) ppm. 13C 15.6 Hz, 18 H, CH3), 1.28 (d, JP,H = 6.8 Hz, 6 H, CH3), 3.69 (m, 1
NMR (CD3CN): δ = 19.3 (s, CH3), 23.1 (s, CH3), 25.6 (s, CH3), H, CH), 4.17 (m, 1 H, CH), 8.11 (d, JP,H = 26.8 Hz, 1 H, CH)
37.4 (d, JC,P = 47 Hz), 62.8 (d, JC,P = 4 Hz, CH), 63.7 (d, JC,P
=
ppm. 13C NMR (CDCl3): δ = 20.1 (s, CH3), 23.0 (s, CH3), 27.7 [s,
(CH3)3], 38.6 (d, JC,P = 54 Hz, C), 46.7 (s, CH), 50.2 (s, CH), 161.4
(s, CH) ppm. C15H33N2PSe (351.37): calcd. C 51.27, H 9.47, N
7.97, P 8.81; found C 51.38, H 9.21, N 8.04, P 8.52.
4 Hz, CH), 120.9 (q, JC,F = 321 Hz, CF3), 171.7 (d, JC,P = 28 Hz,
CH) ppm. C17H35F6N2O6PS2 (572.56): calcd. C 35.66, H 6.16, N
4.89, P 5.41; found C 35.23, H 5.97, N 4.97, P 5.17.
Di-tert-butyl{[(diisopropylamino)methylene]amino}(methylselenyl)-
phosphonium Trifluoromethanesulfonate (10): To a solution of 8
(2.5 mmol) in DCM (5 mL) at –78 °C was added a solution of
methyl trifluoromethanesulfonate (2.5 mmol) in DCM (5 mL) with
stirring. After 15 min, the temperature was increased to 20 °C, and
the solvent was evaporated. The remaining solid was recrystallized
from THF (–20 °C). Yield 1.21 g (94%); m.p. 87–88 °C, white crys-
NЈ-(Di-tert-butylphosphanyl)-N,N-diisopropylformamidine (5): To a
suspension of 3 (5 mmol) in THF (20 mL) cooled to –10 °C was
added a solution of (Me3Si)2NLi (10 mmol) with stirring over
5 min. The reaction mixture was stirred for 10 min, and then the
THF was evaporated. Pentane (15 mL) was added to the residue,
and the solid precipitate was removed by filtration and washed with
pentane. The filtrate was concentrated, and the residue was distilled
to give colorless crystals (1.28 g, 94%); b.p. 60–63 °C/5 Torr, m.p.
1
tals. 31P NMR (CD3CN): δ = 95.3 (JP,Se = 480 Hz) ppm. H NMR
1
37–39 °C. 31P NMR (C6D6): δ = 102.5 ppm. H NMR (C6D6): δ =
(CDCl3): δ = 1.24 (d, JH,H = 7.8 Hz, 3 H, CH3Se), 1.31 (d, JP,H
=
6.6 Hz, 6 H, CH3), 1.35 (d, JP,H = 6.6 Hz, 6 H, CH3), 1.35 (d, JP,H
= 17.1 Hz, 18 H, CH3), 4.02 (m, 1 H, CH), 4.29 (m, 1 H, CH),
7.80 (d, JP,H = 23.4 Hz, 1 H, CH) ppm. 13C NMR (CDCl3): δ = 6
(d, JC,P = 5 Hz, CH3Se), 19.5 (s, CH3), 22.6 (s, CH3), 27.0 [s,
(CH3)3], 41.5 (d, JC,P = 47 Hz, C), 48.5 (s, CH), 52.2 (s, CH), 160.0
0.81 (d, JH,H = 6.9 Hz, 6 H, CH3), 1.12 (d, JH,H = 6.9 Hz, 6 H,
CH3), 1.27 (d, JP,H = 10.5 Hz, 18 H, CH3), 2.97 (m, 1 H, CH), 4.30
(m, 1 H, CH), 8.1 (d, JP,H = 18.0 Hz, 1 H, CH) ppm. 13C NMR
(C6D6): δ = 19.9 (s, CH3), 22.8 (s, CH3), 28.4 (d, JC,P = 14 Hz,
CH3), 32.9 (d, JC,P = 20 Hz, C), 44.8 (s, CH), 47.2 (s, CH), 157.5
(d, JC,P = 39 Hz, CH) ppm. C15H33N2P (272.41): calcd. C 66.14,
H 12.21, N 10.28, P 11.37; found C 65.78, H 12.01, N 10.15, P
11.58.
– +
(s, CH) ppm. MS: m/z = 366 [M – CF3SO3 ] . C17H36F3N2O3PSSe
(515.47): calcd. N 5.43, P 6.01; found N 5.63, P 6.38.
N,N-Diisopropyl-NЈ-(di-tert-butylphosphoroselenoyl)formamidine
Trifluoromethanesulfonate (11): To a solution of 8 (2.5 mmol) in
DCM (5 mL) at –78 °C was added a solution of trifluoromethane-
sulfonic acid (2.5 mmol) in DCM (25 mL) with stirring. After
15 min, the temperature was increased to 20 °C and the mixture
stirred for 10 min. The solvent was evaporated. The remaining
transparent solid was washed with diethyl ether (3ϫ 5 mL) and
dried. Yield 1.13 g (90 %); m.p. 168–169 °C, white crystals. 31P
Di-tert-butyl{[(diisopropylamino)methylene]amino}phosphonium Tri-
fluoromethanesulfonate (6): To a suspension of 3 (25 mmol) in THF
(10 mL) at 20 °C was added a solution of 5 (25 mmol) in THF
(5 mL) with stirring. In 30 min, the 31P NMR spectrum of the reac-
tion mixture exhibited signals at δ = 51 and 63 ppm (JP, H
=
445 Hz). The solvent was evaporated, and diethyl ether (20 mL)
was added. The precipitated solid was collected by filtration,
washed with diethyl ether (3 ϫ 15 mL), and dried. Yield 1.9 g
(90%); m.p. 88–89 °C. 31P NMR (CD3CN): δ = 63 (JP,H = 445 Hz)
1
NMR (CDCl3): δ = 125 (JP,Se = 800 Hz) ppm. H NMR (CDCl3):
δ = 1.37 (d, JH,H = 6.9 Hz, 6 H, CH3), 1.43 (d, JH,H = 6.9 Hz, 6
H, CH3), 1.43 (d, JP,H = 17.7 Hz, 18 H, CH3), 4.0 (m, 1 H, CH),
5.04 (m, 1 H, CH), 9.06 (dd, JP,H = 13.2 Hz, JH,H = 9.6 Hz, 1 H,
CH), 9.48 (m, 1 H, NH) ppm. 13C NMR (CDCl3): δ = 19.5 (s,
CH3), 24.3 (s, CH3), 27.4 [s, (CH3)3], 40.9 (d, JC,P = 38 Hz, C), 50.5
(s, CH), 53.1 (s, CH), 158.2 (d, JC, P = 10 Hz, CH) ppm.
C16H34F3N2O3PSSe (501.44): calcd. N 5.59, P 6.18; found N 5.73,
P 6.01.
1
ppm. H NMR (CD3CN): δ = 1.29 (d, JH,H = 6.9 Hz, 6 H, CH3),
1.30 (d, JH,H = 6.9 Hz, 6 H, CH3), 1.31 (d, JP,H = 16.8 Hz, 18 H,
CH3), 3.86 (m, 1 H, CH), 4.47 (m, 1 H, CH), 6.31 (d, JP,H = 428 Hz,
1 H, PH), 8.03 (d, JP,H = 20.7 Hz, 1 H, CH) ppm. C16H34F3N2O3PS
(422.48): calcd. N 6.63, P 7.33; found N 6.96, P 7.22.
Di-tert-butyl{[(diisopropylamino)methylene]amino}(methyl)phos-
phonium Trifluoromethanesulfonate (7): To a solution of 5
(2.5 mmol) in DCM (5 mL) at –78 °C was added a solution of
methyl trifluoromethanesulfonate (2.5 mmol) in DCM (5 mL) with
stirring. After 10 min, the temperature was increased to 20 °C, and
the solvent was evaporated. The remaining solid was washed with
diethyl ether (2ϫ 5 mL) and dried. Yield 0.88 g (81%); m.p. 78–
79 °C, colorless crystals. 31P NMR (CDCl3): δ = 59 ppm. 1H NMR
General Procedure for the Synthesis of 13a,b: To a suspension of 1b
(5 mmol) in DCM (25 mL) at –20 °C, a solution of (alkylamino)-
phosphane 12 (10 mmol) in DCM (10 mL) was added with stirring.
The solution turned brown. The temperature was increased to
20 °C, and the mixture was stirred for 30 min, during which time
the color faded. The solvent was evaporated in vacuo until the
weight of the residue remained constant. The residue was washed
with diethyl ether (3ϫ 20 mL) to remove iPr2NCHO and dried in
vacuo. Then, it was dissolved in THF (25 mL), and NaH (60% in
oil, 5 mmol) was added portionwise. When the evolution of hydro-
gen had ceased, the solvent was evaporated in vacuo. To the resi-
due, DCM (25 mL) was added, and the solid was collected by fil-
tration and washed with DCM. The filtrate was concentrated to
dryness, and the residue was washed with diethyl ether (3ϫ 10 mL)
to extract (alkylamino)phosphane (90–95%). The residue was dried
in vacuo (0.05 Torr) and recrystallized from THF at –10 °C.
(CDCl3): δ = 1.23 (d, JP,H = 15 Hz, 18 H, CH3), 1.24 (d, JH,H
=
8 Hz, 3 H, CH3), 1.28 (d, JP,H = 6.5 Hz, 6 H, CH3), 1.79 (d, JP,H
= 6.5 Hz, 6 H, CH3), 3.91 (m, 1 H, CH), 4.07 (m, 1 H, CH), 7.92
(d, JP,H = 19 Hz, 1 H, CH) ppm. 13C NMR (CDCl3): δ = 0.4 (d,
JC,P = 42 Hz, CH3), 19.7 (s, CH3), 22.0 (s, CH3), 26.0 [s, (CH3)3],
34.6 (d, JC,P = 62 Hz, C), 46.8 (s, CH), 52.3 (s, CH), 158.6 (s, CH)
– +
ppm. MS: m/z = 287 [M – CF3SO3 ] . C17H36F3N2O3PS (436.51):
calcd. C 46.78, H 8.31, N 6.42, P 7.10; found C 47.11, H 8.47, N
6.37, P 6.89.
N,N-Diisopropyl-NЈ-(di-tert-butylphosphoroselenoyl)formamidine {[(Di-tert-butylphosphanyl)(methyl)amino]methylene}diisopropyl-
(8): To a solution of 5 (2.5 mmol) in benzene (5 mL) was added
ammonium Trifluoromethanesulfonate (13a): 31P NMR (CD3CN): δ
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FULL PAPER
= 116.9 (br. s), 140.3 (br. s), 150.5 (br. s), integral ratio 1:1.3:4.3.
1H NMR (CD3CN): δ = 1.33 (d, JP,H = 13.2 Hz, 18 H, CH3), 1.36
(d, JH,H = 6.3 Hz, 12 H, CH3), 3.55 (s, 3 H, CH3), 4.00 (m, 1 H,
2,2-Di-tert-butyl-3-(dimethylamino)-2,3-dihydro-1H-benzo[d][1,2]-
azaphosphol-2-ium Trifluoromethanesulfonate (16a): White solid,
yield 8.84 g (80 %); m.p. 166–167 °C. 31P NMR (CD3CN): δ =
CH), 4.5–5.5 (m, 1 H, CH), 7.46 (s), 7.90 (d, JH,H = 6.3 Hz, 1 H, 78.4 ppm. 1H NMR (CD3CN): δ = 1.48 (d, JP,H = 15 Hz, 18 H,
CH) ppm. 13C NMR (CD3CN): δ = 19.5 (br. s, CH3), 20.0 (br. s,
CH3), 28.4 [d, JC,P = 16 Hz, C(CH3)3], 35.6 (d, JC,P = 33 Hz, C),
50.4 (s, CH3N), 52.3 (br. s, CH), 160.5 (br. s, CH) ppm. MS: m/z
CH3), 2.45 (s, 6 H, CH3), 5.49 (s, 1 H, CH), 7.03 (t, JH,H = 7.5 Hz,
1 H, CH), 7.09 (d, 1 H, CH), 7.35 (m, 2 H, CH), 7.53 (d, J =
10.5 Hz, 1 H, NH) ppm. 13C NMR (CD3CN): δ = 25.7 (s, CH3),
= 394 [M]+. C17H36F3N2O3PS (436.51): calcd. C 46.78, H 8.31, N 37.5 [d, JC,P = 33 Hz, C(CH3)3], 43.5 (d, JC,P = 4 Hz, CH3N), 68.4
6.42, P 7.10; found C 46.34, H 8.11, N 6.26, P 7.42. Yield 2.11 g,
97%; m.p. 133–136 °C (THF, white crystals).
(d, JC,P = 56 Hz, CH), 113.6 (d, JC,P = 9 Hz, CH), 121.2 (s, CH),
122.7 (d, JC,P = 6 Hz, i-C), 127.9 (d, JC,P = 14 Hz, CH), 130.9 (s,
CH), 145.0 (d, JC,P = 8 Hz, C) ppm. MS: m/z = 293 [M]+.
C18H30F3N2O3PS (442.47): calcd. C 48.86, H 6.83, N 6.33, P 7.00;
found C 49.14, H 6.76, N 6.54, P 6.68.
{[(Di-tert-butylphosphanyl)(isopropyl)amino]methylene}diisopropyl-
ammonium Trifluoromethanesulfonate (13b): 31P NMR (CD3CN): δ
= 118.5 (br. s), 96.0 (br. s) ppm; integral ratio 1:0.6. 1H NMR
(CD3CN): δ = 1.31 (d, JP,H = 13 Hz), 1.33 (d, JH,H = 6.5 Hz, 12
H, CH3), 1.39 (d, JP,H = 13.5 Hz, 18 H, CH3), 1.41 (d, J = 6.5 Hz),
1.45 (d, J = 6.5 Hz), 1.52 (d, J = 6.5 Hz, 18 H, CH3), 4.07 (m, 1
H, CH), 4.09 (m, 1 H, CH), 4.27 (m), 4.41 (m), 5.88 (m, 3 H, CH),
7.57 (s), 7.74 (d, JH,H = 12.0 Hz, 1 H, CH) ppm. 13C NMR
(CD3CN): δ = 18.2 (s, CH3), 19.5 (s, CH3), 23.0 [d, JC,P = 13.0 Hz,
C(CH3)3], 23.2 (s, CH3), 23.9 (s, CH3), 28.9 (d, JC,P = 18 Hz, CH3),
29.4 (d, JC,P = 16 Hz, CH3), 35.5 (d, JC,P = 35 Hz, C), 36.5 (d, JC,P
= 36 Hz, C), 54.3 (s, CH), 54.6 (s, CH), 54.8 (s, CH), 55.8 (d, JC,P
= 11 Hz, CH), 58.3 (d, JC,P = 5 Hz, CH), 158.7 (d, JC,P = 10 Hz,
CH), 159.1 (d, JC,P = 9 Hz, CH) ppm. MS: m/z = 315 [M]+.
C19H40F3N2O3PS (464.56): calcd. C 49.12, H 8.68, N 6.03, P 6.67;
found C 48.87, H 8.92, N 5.74, P 6.99. Yield 2.2 g, 95%, m.p. 115–
117 °C (white crystals, THF).
2,2-Di-tert-butyl-3-(dimethylamino)-5-methyl-2,3-dihydro-1H-benzo-
[d][1,2]azaphosphol-2-ium Trifluoromethanesulfonate (16b): White
solid, yield 8.55 g (75%); m.p. 130–132 °C. 31P NMR (CD3CN): δ
= 79.1 ppm. 1H NMR (CD3CN): δ = 1.44 (d, JP,H = 15.9 Hz, 18
H, CH3), 2.29 (s, 3 H, CH3), 2.41 (d, JP,H = 1.8 Hz, 6 H, CH3),
5.41 (s, 1 H, CH), 6.95 (t, JH,H = 8.7 Hz, 1 H, CH), 7.13 (m, 2 H,
CH), 7.42 (d, JP,H = 11.4 Hz, 1 H, NH) ppm. 13C NMR (CD3CN):
δ = 19.9 (s, CH3), 25.7 (s, CH3), 37.4 [d, JC,P = 32 Hz, C(CH3)3],
43.5 (d, JC,P = 4 Hz, CH3N), 68.4 (d, JC,P = 58 Hz, CH), 113.3 (d,
JC,P = 5 Hz, CH), 122.8 (d, JC,P = 11 Hz, i-C), 130.8 (s, C), 131.4
(s, CH), 142.7 (d, JC,P = 8 Hz, C) ppm. C19H32F3N2O3PS (456.50):
calcd. C 49.99, H 7.07, N 6.14, P 6.78; found C 50.17, H 6.81, N
6.31, P 6.97.
P,P-Di-tert-butyl-N-phenylphosphinoselenoic Amide (18a): 31P
NMR (CDCl3): δ = 95.4 (JP,Se = 763 Hz) ppm. 1H NMR (CDCl3):
δ = 1.44 (d, JP,H = 15.9 Hz, 18 H, CH3), 4.39 (br. s, 1 H, NH), 7.0
(t, JH,H = 7.2 Hz, 1 H, CH), 7.24 (t, JH,H = 8.1 Hz, 2 H, CH), 7.39
(t, JH,H = 8.4 Hz, 2 H, CH) ppm. 13C NMR (CDCl3): δ = 27.9 (d,
JC,P = 3 Hz, CH3), 41.2 (d, JC,P = 44 Hz, C), 121.9 (d, JC,P = 4 Hz,
CH), 122.6 (s, CH), 128.6 (s, CH), 142.0 (d, JC,P = 4 Hz, C) ppm.
MS: m/z = 317 [M]+. C14H24NPSe (316.28): calcd. C 53.17, H 7.65,
N 4.43; found C 53.42, H 7.44, N 4.12. Yield: 90 %; b.p. 180–
183 °C/0.05 Torr, m.p. 153–154 °C.
General Procedure for the Synthesis of 15a,b, 18a–c, and 21a–d:
Bromodi(tert-butyl)phosphane [prepared from di(tert-butyl)chloro-
phosphane and bromotrimethylsilane, 1 equiv.], the corresponding
alkyl(aryl)amine (1.2 equiv.), and triethylamine (1.5 equiv.) were
heated to reflux in pyridine for 1–2 h (15 h for adamantylamine)
until the bromophosphane (δ = 150–153 ppm) was fully consumed
as judged by 31P NMR spectroscopy. The solution was cooled to
room temperature,* the pyridine was evaporated in vacuo, and the
residue was distilled in vacuo (0.05 Torr). *For the synthesis of sele-
nides: To the reaction mixture, selenium (1.1 equiv.) was added, and
the mixture was stirred at room temperature for 1.5 h. The excess
selenium was removed by filtration, the pyridine was evaporated,
and the target selenides were distilled in vacuo (0.05 Torr).
P,P-Di-tert-butyl-N-(4-methylphenyl)phosphinoselenoic Amide
(18b): 31P NMR (CDCl3): δ = 96.1 (JP,Se = 831 Hz) ppm. 1H NMR
(CDCl3): δ = 1.42 (d, JP,H = 15.9 Hz, 18 H, CH3), 2.27 (s, 3 H,
CH3), 4.28 (br. s, 1 H, NH), 7.03 (d, JP,H = 8.4 Hz, 2 H, CH), 7.25
(d, JH,H = 8.4 Hz, 2 H, CH) ppm. 13C NMR (CDCl3): δ = 20.7 (s,
Di-tert-butyl(p-tolylamino)phosphane (15b): 31P NMR (CDCl3): δ =
59.8 ppm. 1H NMR (CDCl3): δ = 1.14 (d, JP,H = 11.7 Hz, 18 H,
CH3), 2.25 (s, CH3), 3.89 (d, JP,H = 10.5 Hz, 1 H, NH), 6.81 (dd,
JH,H = 8.7 Hz, J = 2.4 Hz, 2 H, CH), 6.98 (d, JH,H = 8.4 Hz, 2 H,
CH3), 28.0 (s, CH3), 41.1 (d, JC,P = 45 Hz, C), 122.5 (d, JC,P
=
3 Hz, CH), 132.3 (s, C), 139.1 (d, JC,P = 4 Hz, CH) ppm. MS: m/z
= 331 [M]+. C15H26NPSe (330.31): calcd. C 54.54, H 7.93, N 4.24;
found C 54.21, H 8.17, N 4.64. Yield: 93 %; b.p. 180–183 °C/
0.05 Torr, m.p. 83–84 °C.
CH) ppm. 13C NMR (CDCl3): δ = 20.4 (s, CH3), 28.2 (d, JC,P
=
15 Hz, CH3), 34.2 (d, JC,P = 19 Hz, C), 115.9 (d, JC,P = 11 Hz,
CH), 127.3 (s, C), 129.6 (s, CH), 146.9 (d, JC,P = 16 Hz, C) ppm.
Yield 96%; b.p. 105–110 °C/0.05 Torr.
P,P-Di-tert-butyl-N-(4-methoxyphenyl)phosphinoselenoic Amide
(18c): 31P NMR (CDCl3): δ = 95.7 ppm. 1H NMR (CDCl3): δ =
1.40 (d, JP,H = 15.9 Hz, 18 H, CH3), 3.74 (s, CH3), 4.20 (d, JP,H
=
General Procedure for the Synthesis of 16a,b: To a solution of 1a
(2.5 mmol) in acetonitrile (40 mL) at –10 °C, a solution of 15
(5 mmol) in acetonitrile (30 mL) was added dropwise with stirring
for 15 min. The reaction mixture was stirred at –10 °C for 1 h, the
temperature was increased to 20 °C (the reaction mixture turned
brown), and the mixture was stirred overnight. The reaction mix-
ture turned light yellow. Triethylamine (3 mmol) was added to the
reaction mixture. The solvent was evaporated until the weight was
constant. Compound 15 was extracted from the solid residue with
hexane (3ϫ 30 mL). Yield: 16a: 5.1 g (86%); 16b: 5.65 g (90%).
The remaining residue was dissolved in DCM (20 mL), and the
5.4 Hz, 1 H, NH), 6.77 (d, JH,H = 8.7 Hz, 2 H, CH), 7.27 (d, JH,H
= 8.7 Hz, 2 H, CH) ppm. 13C NMR (CDCl3): δ = 28.0 (s, CH3),
40.9 (d, JC,P = 44 Hz, CH3), 55.5 (s, CH3), 113.8 (s, C), 125.0 (d,
JC,P = 4 Hz, CH), 134.4 (d, JC,P = 4 Hz, C), 155.9 (s, CH) ppm.
C15H26NOPSe (346.31): calcd. C 52.02, H 7.57, N 4.04; found C
51.94, H 7.84, N 4.32. Yield: 98%; b.p. 190–192 °C/0.05 Torr, m.p.
133–134 °C.
General Procedure for the Synthesis of 19a–c: To 1b (5 mmol) at
0 °C was added a solution of 18 (5 mmol) in DMC (30 mL). The
temperature was increased to 20 °C over 15 min, and the reaction
resulting solution was washed with water (3ϫ 20 mL). The organic mixture was stirred for 3 h. The solvent was removed under reduced
layer was separated, and the solvent was evaporated until the
weight was constant. The residue was recrystallized from THF.
pressure. The residue was washed with diethyl ether (3ϫ 20 mL).
The crystalline residue was collected by filtration, washed with
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water (3ϫ 20 mL), dried with P2O5, and then washed with a small
amount of THF.
{[(Di-tert-butylphosphanyl)(4-methylphenyl)amino]meth-
ylene}diisopropylammonium Trifluoromethanesulfonate (20b): 31P
NMR (CD3CN): δ = 137.5 ppm. H NMR (CD3CN): δ = 0.98 (d,
1
{[(Di-tert-butylphosphoroselenoyl)(phenyl)amino]methylene}-
diisopropylammonium Trifluoromethanesulfonate (19a): 31P NMR
JH,H = 6.6 Hz, 6 H, CH3), 1.34 (d, JP,H = 12.9 Hz, 18 H, CH3),
1.46 (d, JH,H = 6.6 Hz, 6 H, CH3), 2.38 (s, 3 H, CH3), 3.69 (m, 1
H, CH), 4.04 (m, 1 H, CH), 7.28 (d, JH,H = 7.8 Hz, 2 H, CH), 7.34
(d, JH,H = 8.7 Hz, 2 H, CH), 7.76 (br. s, 1 H, CH) ppm. 13C NMR
(CD3CN): δ = 17.9 (s, CH3), 20.1 (s, CH3Ar), 23.3 (s, CH3), 28.6
[d, JC,P = 16 Hz, C(CH3)3], 36.5 (d, JC,P = 38 Hz, C), 50.8 (s, CH),
51.8 (s, CH), 126.0 (br. s, CH), 130.9 (s, CH), 139.8 (s, C), 142.0
(br. s, C), 155.7 (br. s, CH) ppm. C23H40F3N2O3PS (512.61): calcd.
C 53.89, H 7.87, N 5.46, P 6.04; found C 54.11, H 7.91, N 5.21, P
6.51. Yield 2.51 g, 98%; m.p. 163–164 °C.
1
(CD3CN): δ = 145.3 (JP,Se = 789 Hz) ppm. H NMR (CD3CN): δ
= 0.96 (d, JH,H = 6.5 Hz, 6 H, CH3), 1.50 (d, JH,H = 6.5 Hz, 6 H,
CH3), 1.52 (d, JP,H = 17.5 Hz, 18 H, CH3), 3.48 (m, 1 H, CH), 4.13
(m, 1 H, CH), 7.62 (m, 5 H, CH), 9.28 (br. s, 1 H, CH) ppm. 13C
NMR (CD3CN): δ = 18.0 (s, CH3), 23.7 (s, CH3), 28.5 (s, CH3),
44.6 [d, JC,P = 28 Hz, C(CH3)3], 52.8 (s, CH), 53.0 (s, CH), 129.4
(s, CH), 130.5 (s, CH), 131.3 (s, CH), 138.1 (s, C), 158.2 (d, JC,P
=
13 Hz, CH) ppm. MS: m/z = 428 [M]+. C22H38F3N2O3PSSe
(577.54): calcd. C 45.75, H 6.63, N 4.85, P 5.36; found C 46.11, H
6.81, N 4.51, P 5.72. Yield 2.8 g, 91%; m.p. 168–169 °C.
{[(Di-tert-butylphosphanyl)(4-methoxyphenyl)amino]methylene}-
diisopropylammonium Trifluoromethanesulfonate (20c): 31P NMR
{[(Di-tert-butylphosphoroselenoyl)(4-methylphenyl)amino]meth-
ylene}diisopropylammonium Trifluoromethanesulfonate (19b): 31P
NMR (CD3CN): δ = 145.4 (JP,Se = 816 Hz) ppm. 1H NMR
1
(CD3CN): δ = 137.9 ppm. H NMR (CD3CN): δ = 1.00 (d, JH,H
= 6.6 Hz, 6 H, CH3), 1.34 (d, JP,H = 12.9 Hz, 18 H, CH3), 1.46 (d,
JH,H = 6.6 Hz, 6 H, CH3), 3.72 (m, 1 H, CH), 3.86 (s, 3 H, CH3),
4.04 (m, 1 H, CH), 7.03 (d, JH,H = 9 Hz, 2 H, CH), 7.33 (d, JH,H
= 9 Hz, 2 H, CH), 7.75 (br. s, 1 H, CH) ppm. 13C NMR (CD3CN):
δ = 18.0 (s, CH3), 23.3 (s, CH3), 28.6 (d, JC,P = 16 Hz, CH3), 36.4
[d, JC,P = 38 Hz, C(CH3)3], 50.7 (s, CH), 51.7 (s, CH), 55.6 (s,
CH3O), 115.4 (s, CH), 127.4 (br. s, CH), 137.0 (br. s, C), 155.6 (br.
s, CH), 159.9 (br. s, C) ppm. C23H40F3N2O4PS (528.61): calcd. C
52.26, H 7.63, N 5.30, P 5.86; found C 52.41, H 7.91, N 5.02, P
6.21. Yield 2.59 g (98%); m.p. 148–149 °C (white crystals).
P,P-Di-tert-butyl-N-methylphosphinoselenoic Amide (21a): 31P
NMR (CDCl3): δ = 103.5 (JP,Se = 739 Hz) ppm. 1H NMR (CDCl3):
δ = 1.33 (d, JP,H = 16 Hz, 18 H, CH3), 1.85 (br. s, 1 H, NH), 2.79
(d, JP,H = 12 Hz, 3 H, CH3) ppm. 13C NMR (CDCl3): δ = 27.8 (d,
(CD3CN): δ = 0.97 (d, JH,H = 7 Hz, 6 H, CH3), 1.49 (d, JH,H
=
7 Hz, 6 H, CH3), 1.50 (d, JP,H = 17 Hz, 18 H, CH3), 2.45 (s, 3 H,
CH3), 3.45 (m, 1 H, CH), 4.08 (m, 1 H, CH), 7.43 (d, JH,H = 8 Hz,
2 H, CH), 7.48 (d, JH,H = 8 Hz, 2 H, CH), 9.28 (br. s, 1 H, CH)
ppm. 13C NMR (CD3CN): δ = 18.01 (s, CH3), 20.3 (s, CH3Ar),
23.7 (s, CH3), 28.5 (s, CH3), 44.4 [d, JC,P = 29 Hz, C(CH3)3], 52.5
(s, CH), 52.9 (s, CH), 128.9 (s, CH), 131.1 (s, CH), 135.2 (s, CH),
142. 4 (s, C), 158. 2 (s, CH) ppm. MS: m/z = 442 [M]+
.
C23H40F3N2O3PSSe (591.57): calcd. C 46.70, H 6.82, N 4.74, P
5.24; found C 46.49, H 6.53, N 4.99, P 5.61. Yield 2.75 g, 93%;
m.p. 163–164 °C.
{[(Di-tert-butylphosphoroselenoyl)(4-methoxyphenyl)amino]meth-
ylene}diisopropylammonium Trifluoromethanesulfonate (19c): 31P
NMR (CDCl3): δ = 145.1 (JP,Se = 816 Hz) ppm. 1H NMR (CDCl3):
δ = 0.99 (d, JH,H = 6.6 Hz, 6 H, CH3), 1.44 (d, JP,H = 17.5 Hz, 18
H, CH3), 1.49 (d, JH,H = 6.6 Hz, 6 H, CH3), 3.60 (m, 1 H, CH),
3.86 (s, CH3), 4.04 (m, 1 H, CH), 7.12 (d, JH,H = 9 Hz, 2 H, CH),
7.47 (d, JH,H = 9 Hz, 2 H, CH), 9.67 (d, JH,H = 7.5 Hz, 1 H, CH)
JC,P = 1 Hz, CH3), 31.0 (d, JC,P = 3 Hz, CH3), 40.2 (d, JC,P
=
47 Hz, C) ppm. MS: m/z = 255 [M]+. C9H22NPSe (254.21): calcd.
C 42.52, H 8.72, N 5.51; found C 42.31, H 9.03, N 5.40. Yield
91%; b.p. 120–122 °C/0.05 Torr, m.p. 114–115 °C (white crystals).
N,P,P-Tri-tert-butylphosphinoselenoic Amide (21c): 31P NMR
ppm. 13C NMR (CD3CN): δ = 18.1 (s, CH3), 23.7 (s, CH3), 28.5 (CDCl3): δ = 89.8 (JP,Se = 748 Hz) ppm. 1H NMR (CDCl3): δ =
(s, CH3), 44.3 [d, JC,P = 28 Hz, C(CH3)3], 52.4 (s, CH), 52.9 (s, 1.29 (d, JP,H = 15.6 Hz, 18 H, CH3), 1.41 (s, 9 H, CH3), 1.73 (br.
CH), 55.7 (s, CH3O), 115.6 (s, CH), 129.8 (s, C), 130.4 (s, CH),
s, 1 H, NH) ppm. 13C NMR (CDCl3): δ = 27.9 (d, JC,P = 1 Hz,
158.4 (d, JH,H = 14 Hz, CH), 161.5 (s, C) ppm. MS: m/z = 458 CH3), 32.9 (d, JC,P = 3 Hz, CH3), 40.1 (d, JC,P = 47 Hz, C), 54.2
[M]+. C23H40F3N2O4PSSe (607.57): calcd. C 45.47, H 6.64, N 4.61,
P 5.10; found C 45.72, H 6.89, N 4.39, P 5.48. Yield 2.88 g, 95%;
m.p. 129–130 °C.
(d, JC,P = 4 Hz, C) ppm. C9H22NPSe (254.21): calcd. C 48.64, H
9.53, N 4.73; found C 48.81, H 9.71, N 4.41. Yield 98%; b.p. 125–
127 °C/0.05 Torr, m.p. 102–104 °C (white crystals).
General Procedure for the Synthesis of 20a–c: To a solution of 19
(5 mmol) in DCM (15 mL) at 20 °C, hexamethylphosphorous tria-
mide was added (5.5 mmol) dropwise with stirring. After 30 min,
the solvent was evaporated to dryness. Dry diethyl ether (40 mL)
was added to the residue. The flask was shaken until a crystalline
solid had formed. The solid was collected by filtration, washed with
diethyl ether, and dried to constant weight in vacuo (0.05 Torr). If
necessary, these compounds can be recrystallized from dry THF.
N-Adamantyl-P,P-di-tert-butylphosphinoselenoic Amide (21d): 31P
NMR (CDCl3): δ = 85.6 (JP,Se = 733 Hz) ppm. 1H NMR (CDCl3):
δ = 1.34 (d, JP,H = 15.5 Hz, 18 H, CH3), 1.61 (br. s, 1 H, NH), 1.64
(m, 6 H, CH2), 2.07 (m, 3 H, CH), 2.13 (m, 6 H, CH2) ppm. 13C
NMR (CDCl3): δ = 27.9 (d, JC,P = 3 Hz, CH3), 30.3 (s, CH), 36.3
(s, CH2), 40.0 (d, JC,P = 39 Hz, C), 45.9 (d, JC,P = 4 Hz, CH2), 54.7
(d, JC,P = 5 Hz, C) ppm. C18H34NPSe (374.41): calcd. C 57.74, H
9.15, N 3.74; found C 57.41, H 8.92, N 3.61. Yield 92%; b.p 180–
182 °C/0.05 Torr, m.p. 168–169 °C (white crystals).
{[(Di-tert-butylphosphanyl)(phenyl)amino]methylene}diisopropyl-
ammonium Trifluoromethanesulfonate (20a): 31P NMR (CDCl3): δ
= 136.6 ppm. 1H NMR (CD3CN): δ = 0.98 (d, JH,H = 6.6 Hz, 6 H,
CH3), 1.35 (d, JP,H = 13.2 Hz, 18 H, CH3), 1.47 (d, JH,H = 6.6 Hz,
4,4-Di-tert-butyl-2,8-dimethyl-7-(propan-2-yl)-5-selena-3,7-diaza-
4-phosphanon-6-ene-4,7-diium Bis(trifluoromethanesulfonate) (22b):
To a suspension of 1b (10 mmol) in DCM (20 mL) at 20 °C, a solu-
tion of 21b (10 mmol) in DCM (20 mL) was added with stirring.
6 H, CH3), 3.65 (m, 1 H, CH), 4.05 (m, 1 H, CH), 7.42 (d, JH,H
=
7.8 Hz, 2 H, CH), 7.51 (m, 3 H, CH), 7.81 (br. s, 1 H, CH) ppm. After 2 h, the solution was cooled to 0 °C and stirred for 30 min.
13C NMR (CD3CN): δ = 17.7 (s, CH3), 23.2 (s, CH3), 28.5 [d, JC,P
= 16 Hz, C(CH3)3], 36.4 (d, JC,P = 38 Hz, C), 50.8 (s, CH), 51.9 (s,
The precipitated solid was collected by filtration, washed twice with
DCM, dried, and recrystallized from DCM. Yield 2.82 g, 52 %;
CH), 126.2 (br. s, CH), 129.2 (br. s, CH), 130.4 (s, CH), 144.5 (br. m.p. 135–137 °C (white crystals). 31P NMR (CD3CN): δ = 108.2
s, C), 155.6 (br. s, CH) ppm. C22H38F3N2O3PS (498.58): calcd. C
53.00, H 7.68, N 5.62, P 6.21; found C 53.13, H 7.61, N 5.71, P
6.49. Yield 2.46 g, 99%; m.p. 171–172 °C (white crystals).
(JP,Se = 354 Hz) ppm. 1H NMR (CD3CN): δ = 1.41 (d, JH,H
=
6.0 Hz, 6 H, CH3), 1.51 (d, JH,H = 6.5 Hz, 6 H, CH3), 1.56 (d, JH,H
= 6.5 Hz, 6 H, CH3), 1.63 (d, JP,H = 19.5 Hz, 18 H, CH3), 4.01 (m,
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Hurieva, I. I. Pervak, S. V. Shishkina, O. V. Shishkin, A. N. Ko-
styuk, Eur. J. Org. Chem. 2012, 4018–4033; c) A. P. Marchenko,
H. N. Koidan, E. V. Zarudnitskii, A. N. Hurieva, A. A. Kiril-
chuk, A. A. Yurchenko, A. Biffis, A. N. Kostyuk, Organometal-
lics 2012, 31, 8257–8264; d) A. P. Marchenko, H. N. Koidan,
I. I. Pervak, A. N. Huryeva, E. V. Zarudnitskii, A. A. Tolma-
chev, A. N. Kostyuk, Tetrahedron Lett. 2012, 53, 494–496.
A. P. Marchenko, H. N. Koidan, A. N. Hurieva, O. V. Gutov,
A. N. Kostyuk, C. Tubaro, S. Lollo, A. Lanza, F. Nestola, A.
Biffis, Organometallics 2013, 32, 718–721.
a) P. Nägele, U. Herrlich (neé Blumbach), F. Rominger, P. Hof-
mann, Organometallics 2013, 32, 181–191; b) E. Kühnel, I. V.
Shishkov, F. Rominger, T. Oeser, P. Hofmann, Organometallics
2012, 31, 8000–8011.
1 H, CH), 4.61 (m, 2 H, CH), 5.78 (m, 1 H, NH), 9.44 (d, JH,H
=
6.5 Hz, 1 H, CH) ppm. 13C NMR (CD3CN): δ = 19.1 (s, CH3),
23.1 (s, CH3), 24.3 (d, JC,P = 5 Hz, CH3), 27.9 (s, CH3), 44.6 [d,
JC,P = 32 Hz, C(CH3)3], 50.8 (d, JC,P = 9 Hz, CH), 62.1 (s, CH),
66.2 (s, CH), 173.5 (s, CH) ppm. C20H41F6N2O6PS2Se (693.60):
calcd. C 34.63, H 5.96, N 4.04; found C 34.24, H 5.65, N 3.89.
[3]
[4]
General Procedure for the Reaction of 21a–d with Alder’s Dimer 1b:
To a suspension of 1b (10 mmol) in DCM (20 mL) at 20 °C, a solu-
tion of 21a–d (10 mmol) in DCM (10 mL) was added with stirring.
For 21a, the reaction mixture was stirred for 30 min (21b: 72 h),
and then the solvent was evaporated to dryness. The residue was
extracted with diethyl ether (4ϫ 30 mL) at 30 °C. The undissolved
crystalline residue was dried in vacuo. For 21c and 21d: After 3 h,
iPr2NEt (10 mmol) was added. The solvent was evaporated to dry-
ness. The residue was extracted with hexane (3ϫ 20 mL). The hex-
ane was evaporated, and the residue was subjected to plate
chromatography on silica gel (DCM) to give 11, Rf = 0.6–0.8.
Yield: 21c: 2.21 g (63%); 21d: 2.77 g, (79%).
[5]
[6]
A. Marchenko, G. Koidan, A. Hurieva, A. Savateev, A. Kos-
tyuk, Tetrahedron Lett. 2013, 54, 5671–5673.
a) R. W. Alder, M. E. Blake, S. Bufali, C. P. Butts, A. G. Orpen,
J. Schütz, S. J. Williams, J. Chem. Soc. Perkin Trans. 1 2001,
1586–1593; b) R. W. Alder, C. P. Butts, A. G. Orpen, J. Am.
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{[(Di-tert-butylphosphoroselenoyl)(methyl)amino]methylene}-
diisopropylammonium Trifluoromethanesulfonate (23a): 31P NMR
[7]
[8]
1
(CDCl3): δ = 143.3 (JP,Se = 808 Hz) ppm. H NMR (CDCl3): δ =
1.37 (d, JH,H = 6.6 Hz, 12 H, CH3), 1.54 (d, JP,H = 17.4 Hz, 18 H,
CH3), 3.85 (d, JH,H = 6 Hz, 3 H, CH3), 4.05 (m, 1 H, CH), 5.04
(m, 1 H, CH), 9.51 (d, JH,H = 9.9 Hz, 1 H, CH) ppm. 13C NMR
(CDCl3): δ = 20.8 (s, CH3), 24.6 (s, CH3), 40.3 (s, NCH3), 43.6 (d,
JC,P = 30 Hz, C), 52.7 (s, CH), 53.3 (s, CH), 160.9 (d, JC,P = 15 Hz,
CH) ppm. C17H36F3N2O3PSSe (515.47): calcd. C 39.61, H 7.04, N [9]
5.43, P 6.01; found C 39.21, H 6.79, N 5.51, P 5.79. Yield 3.81 g
(74%); m.p. 197–198 °C, white crystals.
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H. B. Burgi, J. D. Dunitz in Structure Correlation, Wiley-VCH,
Weinheim, 1994, vol. 2, pp. 741–784.
{[(Di-tert-butylphosphoroselenoyl)(isopropyl)amino]methylene}-
diisopropylammonium Trifluoromethanesulfonate (23b): 31P NMR
(CD3CN): δ 133.5 (br. s) ppm. 1H NMR (CD3CN): δ = 1.45 (d,
JH,H = 6.6 Hz, 6 H, CH3), 1.50 (d, JH,H = 6.6 Hz, 6 H, CH3), 1.57
(d, JP,H = 17.4 Hz, 18 H, CH3), 4.31 (m, 1 H, CH), 4.66 (m, 1 H,
CH), 4.83 (m, 1 H, CH), 8.66 (d, JH,H = 5.7 Hz, 1 H, CH) ppm.
13C NMR (CD3CN): δ = 19.3 (s, CH3), 23.1 (s, CH3), 23.9 (s, CH3),
29.4 (s, CH3), 45.2 (d, JC,P = 43 Hz, C), 55.1 (s, CH), 56.4 (s, CH),
56.8 (s, CH), 161.2 (d, JC,P = 10 Hz, CH) ppm. MS: m/z = 394
[M]+. C19H40F3N2O3PSSe (543.52): calcd. C 41.99, H 7.42, N 5.15,
P 5.70; found C 42.13, H 7.61, N 5.53, P 5.32. Yield 3.2 g (59%);
m.p. 135–136 °C, white crystals.
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[12]
[13]
[14]
Supporting Information (see footnote on the first page of this arti-
cle): Crystallographic data for 3, 13a, 13b, 16, 19a, 20a, 22b, and
23b and detailed calculated data for 13, 19a, 20a, 22b, and 23b.
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M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
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Acknowledgments
The authors thank Dr. V. V. Trachevsky, the Joint Use Center of
NMR Spectroscopy at the G. V. Kurdyumov Institute for Metal
Physics of NAS of Ukraine for recording the NMR spectra. We
also thank the SKIT supercomputer team at the Institute of Cyber-
netic, NAS of Ukraine for providing access to the SKIT computer
cluster for A. B. R. for the ORCA calculations.
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