Transformation Routes of PV- and PIII-N-Substituted Acyclic Diaminocarbenes

Article abstract of DOI:10.1002/ejic.201801141

Herein we report on the synthesis of a set of transient N-(P^III)-phosphanyl and N-(P^V)-phosphoroselenoyl acyclic diaminocarbenes by deprotonation of the corresponding formamidinium salts. It is shown that N-(P^V)-substituted acyclic diaminocarbenes undergo 1,2-phosphorus shift. Transformations of N-(P^III)-substituted acyclic diaminocarbenes result in tetrahydroquinazolines as final products. The proposed mechanism includes the isomerization of the carbenes into transient azomethine ylides followed by their cyclization via electrophilic aromatic substitution. Introduction of the electron-donating dimetylamino group into the phenyl substituent markedly enhances the rate of the reaction and the yield of the final product. In the case of the morpholine derivative, the corresponding azomethine ylide undergoes opening the morpholine ring giving vinyloxazolidin-2-amine. The results are corroborated by DFT calculations.

Full text of DOI:10.1002/ejic.201801141

DOI: 10.1002/ejic.201801141
Full Paper
Carbene Cyclization
V
III
Transformation Routes of P - and P -N-Substituted Acyclic
Diaminocarbenes
[a]
[a]
[a]
[a]
Anatoliy Marchenko, Georgyi Koidan, Anastasiya Hurieva, Yurii Vlasenko,
[a]
[b]
[a]
Alexander B. Rozhenko* Jean-Marc Sotiropoulos, and Aleksandr Kostyuk*
Abstract: Herein we report on the synthesis of a set of tran- azomethine ylides followed by their cyclization via electrophilic
III
V
sient N-(P )-phosphanyl and N-(P )-phosphoroselenoyl acyclic aromatic substitution. Introduction of the electron-donating
diaminocarbenes by deprotonation of the corresponding dimetylamino group into the phenyl substituent markedly en-
V
formamidinium salts. It is shown that N-(P )-substituted acyclic hances the rate of the reaction and the yield of the final prod-
diaminocarbenes undergo 1,2-phosphorus shift. Transforma- uct. In the case of the morpholine derivative, the corresponding
III
tions of N-(P )-substituted acyclic diaminocarbenes result in azomethine ylide undergoes opening the morpholine ring
tetrahydroquinazolines as final products. The proposed mecha- giving vinyloxazolidin-2-amine. The results are corroborated by
nism includes the isomerization of the carbenes into transient DFT calculations.
Introduction
For last two decades NHCs have become the ligands of choice
for a multitude of catalytic processes. As acyclic diaminocarbe-
nes (ADCs) provide broader tuning of important ligand parame-
ters such as carbene angle and steric bulk around the carbene
center, their application in organometallic catalysis is gradually
[
1]
growing. The ADCs are less stable compared to NHCs, mainly
due to their high basicity and nucleophilicity. (A)cyclic diamino
carbenes A are less disposed to dimerization and undergo dif-
ferent routes of decomposition, which are greatly dependent
Figure 1. Transformation pathways for diaminocabenes.
[
2]
on steric encumbrance of the substituents. 1,2-Migrations are
well-established reactions for singlet diaminocarbenes afford-
ing compounds of type B. It has been observed for various
III
V
We have recently studied deprotonation of P - and P -substi-
tuted formamidinium salts to the corresponding carbenes.
[9]
[
3,4]
[5]
[6]
types of substituents such as alkyl,
iminoyl, dialkylamino,
and silicon-containing moi-
Varying substituents at the nitrogen atoms we have found an
optimal substitution pattern that provides kinetic stability to
the carbenes. In particular, N-diisopropylamino-N′-di-tert-butyl-
phosphanyl-N′-(4-R-C H ) aminocarbenes D (R = H, Me, MeO,
[
7–9]
[10,11]
phosphino,
borane groups,
[
12]
eties (Figure 1).
In solution, bis(dimethylamino)carbene degrades, forming a
complex mixture probably via hydrogen migration resulting in
6
4
CF ) have been found to be stable (Figure 2). The lifetime of
3
[
2]
azomethine ylide intermediate C. G. Bertrand reported an
acid-promoted isomerization of a stable amino carbene into a
transient azomethine ylide followed by cyclization into a novel
the carbenes in THF solution (t1/2) averages 14 d at 20 °C. A
further increase of a steric encumbrance at the nitrogen atoms
renders them unstable.
[
13]
[14]
bicyclic compound. It should be noted that both carbenes
[
15]
and azomethine ylides
heterocycles.
are widely used in synthesis of
[
a] Institute of Organic Chemistry, National Academy of Sciences of Ukraine,
Murmanska 5, 02660 Kyiv 94, Ukraine
E-mail: a.kostyuk@yahoo.com
http://www.ioch.kiev.ua
[
b] CNRS/UNIV PAU & PAYS ADOUR, Institut des Sciences Analytiques et
de Physico-Chimie pour l′Environnement et les Matériaux (IPREM, UMR
CNRS 5254), Hélioparc,
Figure 2. Stable carbenes D and object of the study carbenes E.
Herein we report on the study of chemical transformations of
2
Avenue du Président Angot, 64053 Pau Cedex 09, France
III
V
N-(P )- and N-(P )-substituted carbenes E with dimethylamino
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejic.201801141.
group and cyclic amine moieties.
Eur. J. Inorg. Chem. 0000, 0–0
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Results and Discussion
amino group instead of dimethylamino one, gives the corre-
3
1
sponding carbene registered by P NMR signal at δp
=
V
III
1
Synthesis of P - and P -N-Substituted Formamidinium
1
16 ppm ( J
= 749 Hz), which quickly disappeared at room
PSe
Salts
temperature. After deprotonation of salt 4a at low temperature
3
1
(
–70 °C) P NMR spectrum of the reaction mixture exhibited
Deprotonation of tetrasubstituted formamidinium salts is the
most common approach to acyclic carbenes. Formamidinium
and amidinium salts can easily be prepared using a powerful
electrophilic reagent developed by Alder et al. – compounds 2
two signals: one from carbene 6a at δ = 114.2 (6 %) and the
p
main intensive peak from the final phosphane selenide 7a
(94 %). It should be noted that after deprotonation of salts 4a,f
the reaction mixtures contained a small amount of P,P-di-tert-
[
16,17]
(
R = Me, iPr) named in the literature as Alder's dimer.
We
butyl-N-phenylphosphinoselenoic amide 3a (δ = 96 ppm). Its
p
extended this approach on a set of formamides. Compounds 2
were readily prepared in high yields by mixing formamides 1
with triflic acid anhydride in dichloromethane (Scheme 1). The
Alder's dimers usually precipitated as analytically pure com-
pounds, in some cases recrystallization from acetonitrile was
formation probably resulted from the addition of formed
(
Me Si) NH to carbene 6 followed by elimination of 3a.
3 2
Phosphane selenide 7g was readily reduced to the corre-
sponding phosphane 8g using highly nucleophilic tris(morph-
olino)phosphine (Scheme 3).
required. For these species, characteristic low-field signals
1
(
≈ 9 ppm) of CH protons were found in H NMR spectra.
Scheme 1. Synthesis of Alder's dimers 2.
N-Aryl phosphinoselenoic amides 3 reacted readily with
Alder's dimers 2a–e in 1:1 molar ratio giving salts 4a–g in over
V
Scheme 3. Deprotonation of P -N-substituted formamidinium salts 4.
[
18]
31
9
0 % yields.
Their P NMR chemical shift values were in a
1
range 136–143 ppm with the J
coupling constants (814–
A typical behaviour of transient carbenes is their reaction
PSe
1
III
834 Hz) typical for the P=Se double bond. In H NMR spectra with selenium. Reactions of N-(P )-substituted carbenes with
[
19]
CH exhibited as a doublet at 8.45–8.68 ppm with a coupling selenium have been previously shown to be more complex.
13
constant ca. 5 Hz or as a broad singlet. C NMR signals covered Deprotonation of salt 5a in the presence of two equivalents of
2
V
the area 152–156 ppm ( J 4–11 Hz). These P salts were read- selenium resulted in a mixture of phosphane selenide 7a and
CP
ily reduced with hexamethylphosphorus triamide to the corre- compound 10 (Scheme 4). The molecular structure of 10 deter-
III
sponding P formamidinium salts 5a–g (Scheme 2).
mined by single-crystal X-ray diffraction is shown in Figure 3.
Compound 10 was reduced with tris(morpholino)phosphine to
III
[19]
the P derivative 11.
Deprotonation of salt 5a in the pres-
ence of only one equivalent of selenium resulted in a mixture
of three compounds 11/10/7a in ratio 41:45:14, as indicated by
3
1
P NMR spectroscopy.
Scheme 2. Synthesis of formamidinium salts 4 and 5.
V
III
Deprotonation of P - and P -N-Substituted
Formamidinium Salts
Scheme 4. Deprotonation of PIII N-substituted formamidinium salts 5a.
V
Deprotonation of P -N-substituted formamidinium salts 4 led
to the corresponding carbenes 6 that quickly underwent 1,2-
These data support the suggestion that transient carbene 9a
phosphorus shift affording the corresponding phosphane reacts with selenium by two different ways. The reaction at the
selenides 7 in high yields.
phosphorus atom afforded carbene 6a which underwent 1,2-P
[
9]
In our previous article we have found that deprotonation shift giving phosphane selenide 7a. The reaction at the carb-
at –50 °C of the salt analogous to 4a, but bearing diisopropyl- enic atom resulted in selone followed by 1,3-P shift and sub-
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quinazolines 12, as well as phosphanes 8 and tBu PNHPh
2
(Scheme 5).
These compounds form via three different routes. Like carb-
enes 6, carbenes 9 react with (Me Si) NH affording methanetri-
3
2
amine derivatives which decompose giving tBu PNHAr (route
2
1
), or undergo 1,2-P shift affording phosphanes 8 (route 3). The
predominant products are tetrahydroquinazolines 12 (route 2).
At first we studied carbenes 9a–c featuring Me N group. The
2
highest yield of tetrahydroquinazolines 12 was achieved for
carbene 9c bearing an electron-donating group at position 3
of the phenyl moiety. Carbenes 9a,b behaved similarly, with a
higher yield in the case of carbene 9a. These results evidence
that the cyclization rate is limited by the aromatic electrophilic
3
1
substitution. Carbene stability estimated by P NMR in solution
decreases in a row 9a > 9c > 9b (Table 1). Deprotonations of
compounds 5d–f featuring cyclic amino group occurred analo-
gously, but somewhat higher yields of by-products, tBu PNHPh
2
Figure 3. Perspective view of 10. Selected bond lengths [Å] and bond angles
°]: Se(1)–P(1) 2.2851(6), Se(1)–C(1) 1.974(2), Se(2)–P(1) 2.1085(6), N(1)–C(1)
.269(3), N(1)–C(2) 1.405(3), N(2)–C(1) 1.366(3); Se(1)P(1)Se(2) 114.17(3),
P(1)Se(1)C(1) 98.38(7), N(2)C(1)N(1) 120.7(2), Se(1)C(1)N(2) 115.9(2),
Se(1)C(1)N(1) 123.3(2).
and phosphane 8, were observed. Carbene 9d featuring azet-
[
1
idino group gave 25 % of tBu PNHPh and in order to achieve
2
higher yield of cyclic product 12d the reaction mixture was
kept at 4 °C for 17 days. Carbene 9d appeared to be quite
3
1
stable: judging by P NMR spectra the reaction mixture kept
at –10 °C for 5 days still contained 41 % of the carbene.
sequent oxidation with the second equivalent of selenium to
pentavalent derivative 10.
Table 1. Reaction product distribution in deprotonation of salts 5.
High nucleophilicy of the phosphorus atom in carbenes 9
was used for a direct preparation of phosphanes 8 from salts 5.
Deprotonation of 5a in the presence of 20 mol-% of phosphane
selenide 7a resulted in phosphane 8a in high yield. In this reac-
tion carbene 9a removes selenium from phosphane selenide
Compound tBu
2
PNHPh
8
12
Half-life of carbene 9
time (T [°C])
Yield [%]
Yield [%] Yield [%]
5a
5b
12
7
–
2
2
–
12
23
–
70
50
90
54
60
46
–
71 min (20)
21 min (20)
30 min (20)
4 days (–4)
54 min (20)
75 min (20)
10 h (15)
5c
4
7
a to give phosphane 8a and carbene 6a. The latter underwent
5
d
25
18
30
–
1,2-phosphorus shift affording again phosphane selenide 7a.
5
e
5
f
5g
Cyclization of Carbenes 9
We studied stability of carbenes 9 in absence of a trapping
agent. Formation of 9 by deprotonation of salts 5 in THF at
Carbene 9e featuring pyrrolidino group kept at 15 °C for 20 h
31
gave cyclic product 12e in 60 % yield. P NMR monitoring of
carbene 9e revealed that it was quite stable at –78 °C for 1 h
(96 %) and after 15 min at room temp. its content reduced to
3
1
–
90 °C by lithium hexamethyldisilazide was confirmed by
P
NMR (δ = 113–114 ppm). Depending on substituents, carbenes
p
9
afforded new condensed heterocyclic systems – tetrahydro-
8
6 %. The cyclization of carbene 9f involving piperidino group
proceeded with large amounts of the byproducts and was car-
ried out at 0 °C for 7 days.
We investigated whether deprotonation of salt 5f with a
bulkier base increases the yield of cyclic product 12f. The reac-
tion was carried out under the analogous conditions using lith-
3
1
ium bis(tert-butyldimethyl)disilazide. Judging by P NMR spec-
troscopy, carbene 9f was the only product in the reaction
Scheme 5. Cyclization of carbenes 9.
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Scheme 6. Deprotonation of salt 5f with (tBuMe
2 2
Si) NLi.
3
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mixture. The reaction completed in 3 days affording no cyclic the five-membered cycle has an envelope conformation: the
product 12f at all, but only the byproducts: phosphane 8f and atoms C(1), O(1), C(16), C(17) are coplanar within 0.004 Å, and
tBu PNHPh (Scheme 6).
the “corner” C(1)N(2)C(17) forms the angle of 32.0° with this
2
Deprotonation of salt 5g featuring morpholino group gave plane.
rise to quite other type of compound – vinyloxazolidin-2-amine
1
3 (55–60 %), along with phosphane 8g (21–26 %) and
tBu PNHPh (17–19 %) as the byproducts. As the reaction was
2
carried out at low temperature, the ratio of reaction products
depended little on time. Phosphane 8g and tBu PNHPh were
2
3
1
identified by P NMR spectroscopy by adding authentic sam-
ples (Scheme 7).
Scheme 7. Deprotonation of salt 5g featuring morpholino group.
The molecular structure of compounds 12a,c–e, and 13 was
determined by single-crystal X-ray diffraction (Figure 4, Figure 5,
Figure 6, Figure 7, and Figure 8). In the studied molecules the
P(1) atom exhibits pyramidal configuration: the sum of the
bond angles is 320.0(2) (12a), 318.9(2) (12c), 321.7(2) (12d),
Figure 5. Perspective view of 12c. Selected bond lengths [Å] and bond angles
°]: P(1)–N(1) 1.714(1), N(1)–C(1) 1.457(2), N(2)–C(1) 1.454(2); P(1)N(1)C(1)
24.6(1), P(1)N(1)C(2) 120.9(1), N(1)C(1)N(2) 110.2(1).
[
1
320.0(2) (12e), 321.3(3) (13). The six-membered cycle
C(1)N(1)C(2)C(7)C(16)N(2) has the conformation of twist-bath
in 12a and 12c, semi-bath in 12d, semi-chair in 12e. In 13
Figure 4. Perspective view of 12a. Selected bond lengths [Å] and bond angles
[
1
°]: P(1)–N(1) 1.714(2), N(1)–C(1) 1.455(2), N(2)–C(1) 1.456(3); N(1)P(1)C(8)
04.21(9), N(1)P(1)C(1) 104.43(9), C(8)P(1)C(12) 111.4(1), P(1)N(1)C(1) 125.6(1),
Figure 6. Perspective view of 12d. Selected bond lengths [Å] and bond angles
[°]: P(1)–N(1) 1.726(2), N(1)–C(1) 1.471(2), N(2)–C(1) 1.439(3); N(1)P(1)C(8)
103.88(9), N(1)P(1)C(12) 105.85(9), C(8)P(1)C(12) 112.0(1), P(1)N(1)C(1)
124.3(1), N(1)C(1)N(2) 115.1(2).
C(1)N(2)C(16) 108.4(2), C(1)N(2)C(17) 110.6(2), C(16)N(2)C(17) 111.2(2),
N(2)C(1)N(1) 110.9(2).
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Figure 7. Perspective view of 12e. Selected bond lengths [Å] and bond angles
°]: P(1)–N(1) 1.7150(9), N(1)–C(1) 1.452(1), N(2)–C(1) 1.456(2), N(1)–C(2)
[
1
1
1
.410(1); N(1)P(1)C(8) 104.09(5), N(1)P(1)C(12) 104.86(5), C(8)P(1)C(12)
11.01(5), P(1)N(1)C(1) 126.64(8), P(1)N(1)C(2) 120.33(7), N(2)C(1)N(1)
10.74(9).
Figure 8. Perspective view of 13. Selected bond lengths [Å] and bond angles
[°]: P(1)–N(1) 1.734(2), N(2)–C(1) 1.441(3), N(1)–C(1) 1.443(3), O(1)–C(1)
1.427(3); N(1)P(1)C(8) 105.9(1), N(1)P(1)C(12) 105.0(1), C(8)P(1)C(12) 110.4(1),
P(1)N(1)C(1) 125.5(1), N(1)C(1)N(2) 113.0(2).
Scheme 8. Transformation of model carbene 9′.
Figure 9. Calculated reaction pathway for transformation of model carbene 9′.
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DFT Calculations
Cyclization of the carbene 9 is corroborated by studying the
reaction mechanism using DFT calculations. For these simula-
tions we consider models with ethyl groups at nitrogen. The
first step of the reaction is a 1,3-migration of the hydrid anion
Scheme 9. Transformation of carbene 9g.
from the NCH group in carbene 9′ to the carbene carbon atom
2
resulted in the formation of a transient azomethine ylide B
Conclusions
(
Scheme 8, Figure 9). In fact, the NBO charge analysis indicates
III
V
in B negatively charged carbon C1 (D = –0.17) and a charge A set of P - and P -N-substituted formamidinium salts – precur-
depletion on carbon C2 (D = +0.13). Considering the geometry sors to the corresponding carbenes, were synthesized. Their de-
III
V
modification, C1–N distance remains quasi the same (1.369 vs. protonation afforded transient P - and P -N-substituted di-
.362 Å), but the N–C2 bond shortens (from 1.482 to 1.361 Å). aminocarbenes. The latter underwent 1,2-P shift forming C-sub-
1
III
Cyclization of B to 12′ can be described as an electrophilic stituted formamidines. N-(P )-substituted diaminocarbenes fea-
aromatic substitution, with C being a Wehland intermediate. turing acyclic and cyclic substituents indicated higher stability
Finally, a capture of the proton by the anionic carbon C1 affords and in the absence of a trapping agent underwent various
the final product 12′ (Scheme 8).
routes of transformations. The predominant route was 1,3-H mi-
At the first look, the activation energy of the first stage is gration giving an azomethine ylide which underwent electro-
too high for the spontaneously proceeding process. However, a philic aromatic substitution to afford (fused) tetrahydroquin-
contribution of the tunneling mechanism, previously discussed azolines in high yields. The competitive routes led to C-phos-
for the proton 1,2- and 1,3-migrations in carbenes, can signifi- phanyl-substituted formamidines and formation of tBu
PNHPh.
2
[
20,21]
cantly reduce the activation energy of the reaction.
DFT calculations corroborate and describe each step of the pro-
If we consider now a cyclic amino substituted carbene 9g, posed mechanism for the formation of tetrahydroquinazolines.
in the cyclization process previously described for the ethyl de-
rivative, the first step is also an H transfer and not a nucleophilic
attack of oxygen into the carbene p vacant orbital as one could Experimental Section
expect (Scheme 9, Figure 10). The formed intermediate species
B is 13.5 kcal/mol less stable than the starting carbene. After
that, the intracyclic O–C bond opened, followed by a single
Solvents were purified and dried by standard methods. Melting
N–C bond rotation and a cyclization on the C1 atom forming points were determined with an electrothermal capillary melting
General: All procedures with air- and moisture-sensitive com-
pounds were performed under dry argon in flame-dried glassware.
finally molecule 13.
point apparatus. 1H NMR spectra were recorded with a Bruker
Figure 10. Calculated reaction pathway for transformation of carbene 9g.
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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. P NMR spectra were re- with I > 3σ(I) (181 parameters; observed/variable ratio 14.5); for 10
correction was applied. For 12a, the refinement converged to R =
0.0439, Rw = 0.0891, GOF = 0.9245 for observed 2630 reflections
1
3
1
corded with a Varian VXR-300 (121.4 MHz). Chemical shifts (δ) are
to R = 0.0325, R = 0.0246, GOF = 1.1099 for observed 3465 reflec-
1 w
given in ppm downfield relative to internal tetramethylsilane (TMS)
tions with I > 3σ(I) (199 parameters; observed/variable ratio 17.4);
for 12c to R1 = 0.0367, Rw = 0.0349, GOF = 1.0927 for observed
2906 reflections with I > 3σ(I) (208 parameters; observed/variable
ratio 14.0); for 12d to R = 0.0337, R = 0.0334, GOF = 1.0816 for
observed 2909 reflections with I > 3σ(I) (190 parameters; observed/
variable ratio 15.3); for 12e to R1 = 0.0346, Rw = 0.0402, GOF =
1.0119 for observed 3290 reflections with I > 3σ(I) (217 parameters;
observed/variable ratio 15.2); for 13 to R1 = 0.0527, Rw = 0.0511,
GOF = 1.0440 for observed 2912 reflections with I > 3σ(I) (208 pa-
rameters; observed/variable ratio 14.0).
1
13
31
for H and C and external 85 % H PO for P. Chromatography
3
4
was performed on Gerudan SI60 silica gel. Elemental analyses were
performed at the analytical laboratory of the Institute of Organic
Chemistry, National Academy of Sciences of Ukraine.
1
w
Calculations: Calculations were carried out using the Gaussian 09
program[
22]
at the DFT level of theory using B97D functional[23–26]
(
see Supporting Information). All the atoms have been described
[27]
with a 6-31+G(d,p) split-valence basis set.
Geometry optimiza-
tions were carried out without any symmetry restrictions, the nature
of the extrema (minima or TS) was verified with analytical frequency
calculations. All total energies and Gibbs free energies have been
zero-point energy (ZPE) and temperature corrected using unscaled
density functional frequencies. The connection between the transi-
CCDC 1050990 (for 10), 1050989 (for 12a), 1050991 (for 12c),
1050992 (for 12d), 1050993 (for 12e), and 1050994 (for 13) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre.
tion states and the corresponding minima was confirmed by IRC
calculations.[
28,29]
The NPA charges were calculated using the NBO
General Procedure for the Synthesis of Salts 2: To a cooled to
procedure (v. 3.1) implemented in the Gaussian-09 set of pro-
–90 °C solution of trifluoromethanesulfonic anhydride (20 mmol) in
grams.[
30]
dichloromethane (30 mL) a solution of the corresponding forma-
mide (44 mmol) in dichloromethane (30 mL) was added. The reac-
tion mixture was stirred until the temperature rose to 20 °C, and
then for additional 1–2 h. The precipitate was filtered under argon,
washed with dichloromethane (3 × 20 mL) and dried to give pure
target compounds. Analytical samples were obtained by crystalliza-
tion from acetonitrile.
Single-Crystal X-ray Diffraction Analysis: X-ray diffraction analy-
ses were performed with automatic Bruker APEX II (10, 12a, 12c,
1
2d, 12e, 13) diffractometer (graphite-monochromated Mo-K radi-
α
ation, CCD detector, ω-scanning). Crystal data for 10: C H N PSe ,
1
7
29
2
2
M = 450.32, monoclinic, space group P2 /c, a = 7.1459(2),
1
3
b = 33.4887(8), c = 8.6244(2) Å, ꢀ = 106.156(1)°, V = 1982.37(9) Å ,
Z = 4, d = 1.509 g cm , μ = 3.810 mm , F(000) = 912, crystal size
–
3
–1
c
1
,1′-[Oxybis(methan-1-yl-1-ylidene)]diazetidinium Trifluoro-
ca. 0.37 × 0.45 × 0.51 mm. 12a: C H N P, M = 292.4, monoclinic,
1
7 29 2
methanesulfonate (2b): White solid, yield 95 %, m.p. 115–116 °C
space group P2 /n, a = 7.3645(5), b = 30.121(2), c = 8.0414(6) Å,
1
1
(
dec.). H NMR (300 MHz, CD CN): δ = 2.64 (m, 4 H, CH ), 4.75 (dd,
3
–3
3
2
ꢀ
0
= 96.445(4)°, V = 1772.5(2) Å , Z = 4, d = 1.096 g cm , μ =
.150 mm , F(000) = 640, crystal size ca. 0.47 × 0.49 × 0.50 mm.
c
JHH = 7.8 and 8.1 Hz, 4 H, CH ), 4.92 (dd, J = 7.8 and 8.1 Hz, 4 H,
–1
2
3
HH
1
CH ), 8.99 (s, 2 H, CH) ppm. C NMR (125.7 MHz, CD CN): δ = 16.4
2
3
1
2c: C H N P, M = 335.47, triclinic, space group P-1, a = 6.7452(3),
1
9 34 3
(
CH ), 56.6 (CH ), 57.4 (CH ), 120.5 (q, J = 319.4 Hz, CF ), 157.36 (s,
2 2 2 3
b = 12.0437(5), c = 12.6136(4) Å, α = 92.806(2)°, ꢀ = 93.507(2)°, γ =
CH) ppm. C H F N O S (452.35): calcd. C 26.55, H 3.12, N 6.19;
3
–3
10 14 6 2 7 2
1
0
1
03.667(3)°, V = 991.69(7) Å , Z = 2, d = 1.123 g cm , μ =
c
found C 26.81, H 3.46, N 6.42.
–1
.143 mm , F(000) = 368, crystal size ca. 0.19 × 0.28 × 0.49 mm.
2d: C18H29N P, M = 304.42, monoclinic, space group Cc, a =
1,1′-[Oxybis(methan-1-yl-1-ylidene)]dipyrrolidinium Trifluoro-
2
1
1
3.0006(5), b = 10.3916(4), c = 13.8342(6) Å, ꢀ = 108.698(2)°, V = methanesulfonate (2c): White solid, yield 90 %, m.p. 198–199 °C
3
–3
–1
1
770.3(1) Å , Z = 4, d = 1.142 g cm , μ = 0.152 mm , F(000) = 664, (dec.). H NMR (500 MHz, CD CN): δ = 2.19 (s, 8 H, 2 CH ), 4.08 (s,
3 2
c
1
3
crystal size ca. 0.14 × 0.26 × 0.40 mm. 12e: C H N P, M = 318.44,
triclinic, space group P1¯ , a = 6.6188(2), b = 11.0049(3), c =
4 H, CH
(125.7 MHz, CD
3.9591(4) Å, α = 66.866(1)°, ꢀ = 78.571(1)°, γ = 82.026(1)°, V = (CH ), 120.8 (q, J = 321 Hz, CF
2
), 4.22 (s, 4 H, CH
CN): δ = 23.5 (CH
), 157.9 (s, CH) ppm. C12H F N O S
18 6 2 7 2
2
), 9.34 (s, 2 H, CH) ppm. C NMR
1
9 31 2
), 24.3 (CH ), 52.3 (CH ), 54.5
3
2
2
2
1
9
3
3
2
3
3
–3
–1
14.38(5) Å , Z = 2, d = 1.157 g cm , μ = 0.150 mm , F(000) = (480.41): calcd. C 30.0, H 3.78, N 5.83; found C 30.18, H 3.91, N 5.52.
c
48, crystal size ca. 0.29 × 0.31 × 0.49 mm. 13: C H N OP, M =
1
9
31
2
1,1′-[Oxybis(methan-1-yl-1-ylidene)]dipiperidinium Trifluoro-
34.44, triclinic, space group P1<Ü->, a = 9.1654(4), b = 9.2614(4),
methanesulfonate (2d): White solid, yield 98 %, m.p. 225–227 °C
c = 12.5550(6) Å, α = 82.902(3)°, ꢀ = 68.606(2)°, γ = 74.214(2)°, V =
1
(
dec.). H NMR (300 MHz, CD CN): δ = 1.80 (m, 4 H, CH ), 1.94 (m,
3
2
3
–3
–1
9
54.51(8) Å , Z = 2, d = 1.164 g cm , μ = 0.151 mm , F(000) =
13
c
8 H, CH ), 4.03 (m, 8 H, CH ), 9.20 (s, 2 H, CH) ppm. C NMR
2 2
3
64, crystal size ca. 0.17 × 0.27 × 0.33 mm. The intensities of 15176
(
125.7 MHz, CD CN): δ = 21.8 (s), 24.6 (s), 25.3 (s), 50.1 (s), 54.9 (s),
3
(10), 17464 (12a), 14440 (12c), 8642 (12d), 10631 (12e), 12934 (13)
1
20.8 (q, JCF = 319 Hz, CF ), 157.9 (s, CH) ppm. C H F N O S
3 14 22 6 2 7 2
reflections were measured at 173(1) K (for 10, 12a, 12d, 12e, 13)
and 123(1) K (for 12c) on a Bruker Smart Apex II diffractometer
operating in the ω and ꢀ scans mode. 4023 (10), 3647 (12a), 4098
(508.46): calcd. C 33.07, H 4.36, N 5.51; found C 32.85, H 4.13, N
5.68.
4
,4′-[Oxybis(methan-1-yl-1-ylidene)]dimorpholin-4-ium Tri-
(
0
(
12c), 3426 (12d), 3814 (12e), 3975 (13) unique reflections [Rint
.030 (10), 0.050 (12a), 0.041 (12c), 0.031 (12d), 0.021 (12e), 0.033
13)] were used in further refinement. Data were corrected for Lo-
=
fluoromethanesulfonate (2e): White solid, yield 98 %, m.p. 196–
1
1
97 °C (dec.). H NMR (500 MHz, CD CN): δ = 3.97 (dt, J = 14.7,
3 1
J = 5.4 Hz, 8 H, 4CH ), 4.09–4.23 (m, 8 H, 4CH ), 9.36 (s, 2 H, CH)
2
2
2
rentz and polarization effects. The structure was solved by direct
methods and refined by the full-matrix least-squares technique in
the anisotropic approximation for non-hydrogen atoms using the
13
ppm. C NMR (125.7 MHz, CD CN): δ = 49.5 (CH ), 53.3 (CH ), 64.8
3
2
2
(
CH ), 65.5 (CH ), 120.8 (q, J = 321 Hz, CF ), 159.0 (CH) ppm.
2 2 3
[31]
C H F N O S (521.41): calcd. C 28.13, H 3.54, N 5.47; found C
12 18 6 2 9 2
SHELXS97 and SHELXL97 programs and CRYSTALS program pack-
[
32]
28.37, H 3.82, N 5.21.
age.
Hydrogen atoms were located in the difference Fourier
maps and refined with fixed positional and thermal parameters. The
Compound 3c was prepared using the procedure described in the
literature.
Chebychev[ weighting Scheme was used. The SADABS absorption
33]
[18]
Eur. J. Inorg. Chem. 0000, 0–0
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Full Paper
P,P-Di-tert-butyl-N-(3-dimethylaminophenyl)phosphinoselenoic
Amide (3c): White solid, yield 86 %, m.p. 103–104 °C (hexane). H
CH ), 4.59 (m, 2 H, CH ), 7.38 (d, J = 7.0 Hz, 2 H, Ph), 7.48–7.55 (m,
2
2
1
13
3 H, Ph) ppm. C NMR (125.7 MHz, CD CN): δ = 16.4 (CH ), 28.4
3 2
NMR (500 MHz, CDCl ): δ = 1.43 (d, J = 16 Hz, 18 H, CH ), 2.94 (s, (CH ), 44.0 (d, J = 29 Hz, C), 57.2 (CH ), 57.7 (CH ), 129.0 (CH), 130.9
3
PH
3
3
2
2
6
H, NCH ), 4.32 (br. s, 1 H, NH), 6.37 [d, J(H,H) = 7 Hz, 1 H, CH], 6.54
(CH), 131.9 (CH), 134.7 (ipso-C), 153.0 (d, J = 4 Hz, C=N), (CF not
3
3
detected) ppm. 31P{ H}NMR (202.4 MHz, CD CN): δ = 136.5 (d, J
1
=
(d, JH,H = 7.5 Hz, 1 H, CH), 7.06 (dd, J = 8 Hz, 1 H, CH), 7.15 (s, 1
HH
3
PSe
13
H, CH) ppm. C NMR (125.7 MHz, CDCl ): δ = 27.6 (s, CH ), 40.3 (s,
828 Hz) ppm. C19H30F N O PSSe (533.46): calcd. N 5.25, P 5.81;
3
3
3 2 3
NCH ), 40.9 (d, J = 44 Hz, C), 105.7 (d, JCP = 4 Hz, CH), 106.6 (s,
found N 5.51, P 5.43.
-{[(Di-tert-butylphosphoroselenoyl)(phenyl)amino]methyl-
3
CP
CH), 109.2 (d, JCP = 4 Hz, CH), 128.7 (s, CH), 142.7 (d, J = 5 Hz, C),
CP
1
31
1
7
5
50.6 (s, C) ppm. P NMR (202.4 MHz, CDCl ): δ = 94.0 (J
59 Hz) ppm. MS: m/z = 359 [M] . C H N PSe (359.36): calcd. C
=
3
PSe
ene}pyrrolidinium Trifluoromethanesulfonate (4e): White solid,
+
1
6 29 2
1
yield 93 %, m.p. 231–233 °C. H NMR (300 MHz, CD CN): δ = 1.56
3
3.48, H 8.13, N 7.80; found C 53.84, H 8.34, N 7.94.
[
d, J = 17 Hz, 18 H, C(CH ) ], 1.75 (m, 2 H, CH ), 1.86 (m, 2 H, CH ),
3 3 2 2
2
.60 (dd, J = 6.6 and 6.9 Hz, 2 H, CH ), 3.99 (dd, J = 6.6 and 6.9 Hz,
2
General Method for the Synthesis of Compounds 4: To a cooled
solution (–78 °C) of the corresponding Alder's dimer (10 mmol) in
dichloromethane (25 mL) a solution of P,P-di-tert-butyl-N-phenyl-
phosphinoselenoic amide (10.3 mmol) in dichloromethane (25 mL)
was added. The reaction mixture was stirred until the temperature
rose to 20 °C. The solvent was removed under reduced pressure.
Ether or THF (30 mL) was added to the residue, and the insoluble
precipitate was filtered off under argon, washed with THF (3 ×
2
H, CH ), 7.54–7.40 (m, 5 H, Ph), 8.54 (d, J = 4 Hz, 1 H, CH) ppm.
2
13
C NMR (125.7 MHz, CD CN): δ = 23.0 (CH ), 25.3 (CH ), 28.4 (CH ),
3
2
2
3
4
4.3 (d, J = 29 Hz, C), 128.7 (CH), 130.6 (CH), 131.7 (d, J = 1.3 Hz,
31
1
CH), 135.9 (ipso-C), 152.8 (d, J = 8.8 Hz, C=N) ppm. P{ H} NMR
(202.4 MHz, CD CN): δ = 139.8 (J = 830 Hz) ppm. ESI-MS: m/z =
3 PSe
+
3
99.2 [M] . C H F N O PSSe (547.48): calcd. N 5.12, P 5.66; found
20 32 3 2 3
N 4.93, P 5.17.
2
0 mL) and dried in vacuo to give 4.
1-{[(Di-tert-butylphosphoroselenoyl)(phenyl)amino]methyl-
ene}piperidinium Trifluoromethanesulfonate (4f): White solid,
N-{[(Di-tert-butylphosphoroselenoyl)(phenyl)amino]methyl-
ene}-N-methylmethanaminium Trifluoromethanesulfonate (4a):
White solid, yield 93 %, m.p. 201–202 °C (dec.). H NMR (500 MHz,
1
yield 86 %, m.p. 212–214 °C. H NMR (300 MHz, CDCl ): δ = 1.29 (m,
3
1
2 H, CH ), 1.53 [d, J = 18 Hz, 20 H, C(CH ) + CH ], 1.83 (m, 2 H,
2 3 3 2
CH ), 2.82 (m, 2 H, CH ), 3.89 (m, 2 H, CH ), 7.3–7.6 (m, 5 H, ArH),
2
2
2
CD CN): δ = 1.60 [d, J = 19 Hz, 18 H, C(CH ) ], 2.44 (s, 3 H, NCH ),
3
3 3
3
13
8
.68 (d, J = 5 Hz, 1 H, CH) ppm. C NMR (125.7 MHz, CDCl ): δ =
3
3
.47 (s, 3 H, NCH ), 7.45 (d, J = 6.5 Hz, 2 H, Ph), 7.53–7.57 (m, 3 H,
3
1
3
22.6 (s, CH
2
), 25.2 (s, CH
2
), 26.9 (s, CH ), 29.3 (s, CH ), 44.9 (d, J =
2 3
Ph), 8.45 (br. s, 1 H, CH) ppm. C NMR (125.7 MHz, CD CN): δ =
3
2
8 Hz, C), 49.7(s, CH ), 59.8(s, CH ), 121 (q, J = 321 Hz, CF SO ),
2
2
3
3
2
8.4 (CH ), 40.2 (CH ), 44.5 (d, J = 29 Hz, C), 129.1, 130.6, 131.2 (d,
3 3
1
29.8 (s, CH), 130.0 (s, CH), 130.9 (s, CH), 136.5 (s, ipso-C), 155.1 (d,
J = 1.3 Hz, CH), 135.7 (ipso-C), CF signal not assigned, 156.0 (d, J =
3
31
31
J = 10 Hz, CH) ppm. P NMR (81 MHz, CDCl
834 Hz) ppm. C21 PSSe (561.51): calcd. N 4.99, P 5.52;
found N 5.31, P 5.83.
3
): δ = 141 (JPSe =
8
.8 Hz, C=N). P NMR (CD CN, 121.4 MHz): δ = 141.2 (J = 814 Hz)
3 PSe
19
H F N O
34 3 2 3
ppm. F NMR (CD CN, 188.1 MHz): δ = –78.0 ppm. MS: m/z = 373.2
M – TfO ] 100 %. C H F N O PSSe (521.45): calcd. N 5.37, P 5.94;
3
–
+
[
18 30 3 2 3
found N 5.73, P 6.23.
4-{[(Di-tert-butylphosphoroselenoyl)(phenyl)amino]methyl-
ene}morpholin-4-ium Trifluoromethanesulfonate (4g): White
N-{[(Di-tert-butylphosphoroselenoyl)(4-methylphenyl)amino]-
methylene}-N-methylmethanaminium Trifluoromethanesulfon-
ate (4b): White solid, yield 90 %, m.p. 198–199 °C (dec.). H NMR
1
solid, yield 90 %, m.p. 183–184 °C. H NMR (500 MHz, CD CN): δ =
3
1
.60 [d, J = 17.5 Hz, 18 H, C(CH ) ], 2.77 (m, 2 H, CH ), 3.44 (m, 2 H,
3 3 2
1
CH ), 3.89 (s, 4 H, 2CH ), 7.48 (d, J = 7.0 Hz, 2 H, Ph), 7.59–7.56 (m,
2
2
(
300 MHz, CD CN): δ = 1.55 [d, J = 17.4 Hz, 18 H, C(CH ) ], 2.39 (s,
13
3
3 3
3
H, Ph), 8.61 (br. s, 1 H, CH) ppm. C NMR (125.7 MHz, CD CN):
3
3
8
H, CH ), 2.42 (s, 3 H, NCH ), 3.42 (s, 3 H, NCH ), 7.30 (s, 4 H, CH ),
3 3 3 Ar
δ = 28.5 (CH ), 44.8 (d, J = 29 Hz, C), 49.5 (CH ), 57.3 (CH ), 64.5
3
2
2
1
3
.45 (d, J = 4.8 Hz, 1 H, CH) ppm. C NMR (125.74 MHz, CD CN):
3
(
1
1
CH ), 66.2 (CH ), 129.9 (CH), 130.1 (CH), 131.0 (CH), 136.4 (ipso-C),
2 2
δ = 20.3 (CH ), 28.5 (CH ), 40.1 (CH ), 44.4 (d, J = 28.9 Hz, C), 49.2
31
1
3
3
3
55.8 (d, J = 10 Hz, C=N) ppm. P{ H} NMR (202.4 MHz, CD CN): δ =
3
(
(
1
–
CH ), 129.6 (CH), 130.9 (d, J = 2.5 Hz, CH), 132.95 (ipso-C), 141.3
19
3
43 (JPSe = 830 Hz) ppm. F NMR (122 MHz, CDCl ): δ = –79 ppm.
3
3
1
ipso-C), 156.25 (d, J = 8.8 Hz, C=N) ppm. P NMR (CD CN,
3
C H F N O PSSe (563.48): calcd. N 4.97, P 5.50; found N 4.71, P
20 32 3 2 4
1
9
21.5 MHz): δ = 141.0 ppm. F NMR (CD CN, 188.1 MHz): δ =
3
5.82.
77.9 ppm. C H F N O PSSe (535.46): calcd. N 5.23, P 5.78; found
19 32 3 2 3
General Method for the Synthesis of Compounds 5: To a suspen-
sion of 5 (8 mmol) in dichloromethane (20 mL) at 20 °C hexamethyl-
phosphorous triamide was added (1 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 formed. The solid was separated by filtration,
washed with diethyl ether, and dried to constant weight in vacuo
N 5.41, P 5.97.
N-{[(Di-tert-butylphosphoroselenoyl)(3-dimethylaminophenyl)-
amino]methylene}-N-methylmethanaminium Trifluoromethane-
sulfonate (4c): White solid, yield 81 %, m.p. 180–182 °C (CH CN).
3
1
H NMR (300 MHz, CD CN): δ = 1.53 [d, J = 17.1 Hz, 18 H, C(CH ) ],
3
3 3
2
.53 (s, 3 H, NCH ), 2.95 (s, 6 H, NCH ), 3.40 (s, 3 H, NCH ), 6.65 (s, 1
3 3 3
H, Ar), 6.72 (d, J = 8.1 Hz, 1 H, Ar), 6.85 (d, J = 7.2 Hz, 1 H, Ar), 7.28
(0.05 Torr).
(
(
dd 1 H, J = 8.4 Hz, Ar), 8.70 (d, 1 H, J = 5.1 Hz, CH) ppm. 13C NMR
125.7 MHz, CD CN): δ = 28.1 (CH ), 39.0 (CH ), 39.1 (CH ), 44.0 (d,
N-{[(Di-tert-butylphosphanyl)(phenyl)amino]methylene}-N-
3
3
3
3
methylmethanaminium Trifluoromethanesulfonate (5a): White
J = 29 Hz, C), 48.6 (CH ), 113.5 (d, J = 13 Hz, CH), 116.9 (s, C), 129.2
3
1
solid, yield 92 %, m.p. 107–109 °C (CH CN). H NMR (500 MHz,
3
(
s, CH), 136.6 (C), CF signal not assigned, 156.8 (d, J = 11.3 Hz, C=
3
CD CN): δ = 1.36 (d, J = 13.0 Hz, 18 H, tBu), 2.52 (s, 3 H, NMe), 3.44
3
1
3
N) ppm.
P NMR (CD CN, 121.4 MHz): δ = 140.1 ppm.
3
(
7
s, 3 H, NMe), 7.43–7.46 (m, 3 H, CHPh), 7.50–7.54 (m, 2 H, CHPh),
C H F N O PSSe (564.51): calcd. N 7.44, P 5.49; found N 7.37, P
20
35
3
3
3
13
.88 (br. s, 1 H, N = CH) ppm. C NMR (125 MHz, CD CN): δ = 28.0
3
5
.71.
(
CH ), 36.0 (d, J = 36.5 Hz, C), 39.7 (CH ), 46.6 (CH ), 120.8 (q, J =
3
3
3
1
-{[(Di-tert-butylphosphoroselenoyl)(phenyl)amino]-methyl-
321 Hz, CF ), 126.8 (CH), 128.2 (CH), 129.4 (CH), 142.7 (br. s, ipso-C),
3
31
ene}azetidinium Trifluoromethanesulfonate (4d): White solid,
yield 98 %, m.p. 249–250 °C (dec.). H NMR (500 MHz, CD CN): δ =
157.0 (br. d, J = 26.4 Hz, N = C) ppm. P NMR (121.4 MHz, CD CN):
3
1
19
δ = 132.9 ppm. F NMR (188.1 MHz, CD CN): δ = –78.0 ppm.
3
3
1
.55 (d, JPH = 18 Hz, 18 H, CH ), 2.00 (m, 2 H, CH ), 3.34 (m, 2 H,
C H F N O PS (442.49): calcd. N 6.33, P 7.00; found N 6.36, P 7.23.
18 30 3 2 3
3
2
Eur. J. Inorg. Chem. 0000, 0–0
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Full Paper
N-{[(Di-tert-butylphosphanyl)(4-methylphenyl)amino]methyl-
(CH), 130.3 (CH), 156.5 (br. s, C=N) ppm. 31P NMR (CD CN,
3
ene}-N-methylmethanaminium Trifluoromethanesulfonate (5b):
80.95 MHz): δ = 134.3 ppm. C H F N O PS (484.52): calcd. N 5.78,
P 6.39; found N 5.76, P 6.36.
2
0 32 3 2 4
1
White solid, yield 93 %, m.p. 156–159 °C (CH CN). H NMR (300 MHz,
3
CD CN): δ = 1.55 (d, J = 13.0 Hz, 17 H, tBu), 2.40 (s, 3 H, Me), 2.42
3
General Procedure for the Synthesis of Compounds 7: To a sus-
pension of P salt 4 (2 mmol) in THF (6 mL) at –90 °C a solution of
(
1
s, 3 H, NMe), 3.42 (s, 3 H, NMe), 7.30 (s, 4 H, CH), 8.44 (d, J = 5 Hz,
V
H, N = CH) ppm. 3 P NMR (121.4 MHz, CD CN): δ = 133.0 ppm.
1
3
lithium hexamethyldisilazide (2 mmol) in THF (6 mL) was added
with stirring over 5 min. The bath temperature was risen to –50 °C
over 2 h, and then it was warmed slowly to ambient temperature.
Insoluble solid was filtered off, the solvent was evaporated, and the
residue was extracted with hexane (20 mL), the solution obtained
was concentrated and the crude product was recrystallized from
hexane (3–5 mL).
C H F N O PS (456.51): calcd. N 6.14, P 6.78; found N 6.43, P 7.24.
19 32 3 2 3
N-{[(Di-tert-butylphosphanyl)(3-dimethylaminophenyl)amino]-
methylene}-N-methylmethanaminium Trifluoromethanesulfon-
1
ate (5c): White solid, yield 92 %, m.p. 107–109 °C (CH CN). H NMR
3
(
500 MHz, CD CN): δ = 1.35 (d, J = 9.0 Hz, 18 H, tBu), 2.60 (s, 3 H,
3
NMe), 2.96 (s, 6 H, NMe), 3.41 (s, 3 H, NMe), (m, 3 H, Ar), 6.63 (s, 1
H, Ar), 6.66 (d, J = 7 Hz, 1 H, Ar), 6.75 (d, J = 7 Hz, 1 H, Ar), 7.27 (dd
1
1
,1-Di-tert-butyl-N,N-dimethyl-N′-(phenyl)phosphanylcarbox-
H, J = 8.5 Hz, Ar), 7.81 (br. s, 1 H, N = CH) ppm. 1 C NMR (125 MHz,
3
imidamide Selenide (7a): Yellow crystals, yield 73 %, m.p. 127–
CD CN): δ = 28.0 (CH ), 36.0 (d, J = 36.5 Hz, C), 39.7 (CH ), 46.6
1
3
3
3
128 °C. H NMR (300 MHz, CDCl ): δ = 1.53 (d, J = 15.9 Hz, 18 H,
3
(
1
CH ), 120.8 (q, J = 320.6 Hz, CF ), 126.8 (CH), 128.2 (CH), 129.4 (CH),
42.7 (br. s, ipso-C), 157.0 (br. d, J = 26.4 Hz, N = C) ppm. P NMR
3
3
CH ), 2.85 (s, 6 H, CH ), 6.73 (d, J = 7.5 Hz, 2 H, CH), 7.01 (t, J =
7
3
3
31
13
.5 Hz, 1 H, CH), 7.29 (t, J = 7.8 Hz, 2 H, ArH) ppm. C NMR
(
121.4 MHz, CD CN): δ = 130.3 ppm. C H F N O PS (485.55): calcd.
3 20 35 3 3 3
(125.7 MHz, CDCl ): δ = 28.7 (s, CH ), 40.8 (d, J = 30.2 Hz, C), 43.23
3
3
N 8.65, P 6.38; found N 8.89, P 6.67.
(s, CH ), 43.24 (s, CH ), 120.6 (s, CH), 122.9 (s, CH), 128.9 (s, CH),
3 3
3
1
148.5 (d, J = 16.3 Hz, ipso-C), 155.5 (d, J = 100.6 Hz, CN) ppm.
P
1
-{[(Di-tert-butylphosphanyl)(phenyl)amino]methylene}azet-
NMR (202.4 MHz, CDCl ): δ = 76.9 (J
149.2 [M – tBu PSe] . C H N PSe (371.36): calcd. C 54.98, H 7.87,
N 7.54; found C 55.17, H 7.99, N 7.71.
= 702 Hz) ppm. MS: m/z =
idinium Trifluoromethanesulfonate (5d): White solid, yield 96 %,
3
PSe
+
1
m.p. 172–173 °C (CH CN). H NMR (300 MHz, CDCl ): δ = 1.33 [d,
2
17 29 2
3
3
ꢁ
JPH = 13.2 Hz, 18 H, C(CH ) ], 2.22 (m, 2 H, CH ), 3.44 (t, J = 7.8 and
3 3
2
α
α
8
(
.1 Hz, 2 H, CH ), 4.57 (t, J = 7.8 and 8.1 Hz, 2 H, ′CH ), 7.48–7.39
2
2
N-[Azetidin-1-yl(di-tert-butylphosphoroselenoyl)methylidene]-
aniline (7d): White crystals, yield 78 %, m.p. 137–138 °C. H NMR
(500 MHz, CDCl ): δ = 1.55 (d, J = 16 Hz, 18 H, CH ), 2.00 (m, 2 H,
CH ), 4.28 (br. s, 4 H, CH ), 6.80 (d, J = 8.0 Hz, 2 H, CH), 6.92 (t, J =
1
3
m, 5 H, HPh), 7.78 (s, 1 H, CH) ppm. C NMR (125.7 MHz, CDCl3):
1
δ = 16.5, 28.5 (d, J = 16.3 Hz CH ), 36.1 (d, J = 35.2 Hz, C), 56.4
3
3
3
(
1
CH ), 56.9 (CH ), 128.4 (d, J = 3.8 Hz, CH), 129.2 (CH), 129.5 (CH),
40.5 (br. s, ipso-C), 154.3 (br. s, C=N) ppm. P NMR (202.4 MHz,
2 2
2
2
3
1
13
7
.5 Hz, 1 H, CH), 7.19 (t, J = 8 Hz, 2 H, ArH) ppm. C NMR
CDCl ): δ = 130.3 (br. s) ppm. C H F N O PS (454.5): calcd. N 6.16,
3
19 30 3 2 3
(125.7 MHz, CDCl ): δ = 17.7 (s, CH ), 28.5 (d, J = 1.3 Hz, CH ), 40.5
3
2
3
P 6.82; found N 6.31, P 7.02.
(d, J = 32.7 Hz, C), 58.35 (s, CH ), 58.37 (s, CH ), 120.7 (s, CH), 121.6
2 2
(
s, CH), 128.0 (s, CH), 145.7 (d, J = 96.8 Hz, CN), 148.8 (d, J = 19 Hz,
1
-{[(Di-tert-butylphosphanyl)(phenyl)amino]methylene}pyrr-
31
1
ipso-C), ppm. P NMR (202.4 MHz, CDCl ): δ = 70.6 ( J = 698 Hz)
ppm. MS: m/z = 385 [M + 2H] 100 %. C H N PSe (383.37): calcd.
C 56.39, H 7.62, N 7.31; found C 56.25, H 7.66, N 7.45.
olidinium Trifluoromethanesulfonate (5e): White solid, yield
3
PSe
+
1
9
8 %, m.p. 140–142 °C (CH CN). H NMR (500 MHz, CD CN): δ = 1.37
18 29 2
3
3
[d, J = 13.0 Hz, 18 H, C(CH ) ], 1.82 (m, 2 H, CH ), 1.90 (m, 2 H, CH ),
3 3 2 2
2
.71 (t, J = 6.0 Hz, CH ), 4.00 (t, J = 6.0 Hz, CH ), 7.50–7.46 (m, 5 H,
2 2
N-[Pyrrolidin-1-yl(di-tert-butylphosphoroselenoyl)methyl-
idene]aniline (7e): White crystals, yield 93 %, m.p. 158–159 °C. H
1
3
HPh), 8.07 (br. s, 1 H, CH) ppm. C NMR (125.74 MHz, CD CN): δ =
2
C), 50.5 (CH ), 56.3 (CH ), 127.9 (d, J = 3.8 Hz, CH), 121.3 (q, J =
1
3
3.1 (CH ), 25.2 (CH ), 28.5 (d, J = 16.4 Hz, CH ), 36.3 (d, J = 36.5 Hz,
2 2 3
NMR (500 MHz, CDCl ): δ = 1.53 (d, J = 16 Hz, 18 H, CH ), 1.66 (m,
3
3
2
2
4 H, CH ), 3.58 (m, 4 H, CH ), 6.73 (dd, J = 8.1, J = 1.2 Hz, 2 H, CH),
2 2
3
20.6 Hz, CF ), 128.8 (CH), 129.5 (CH), 143.0 (br. s, ipso-C), 154.6 (br.
13
3
6.93 (m, 1 H, CH), 7.23 (t, J = 8.1 Hz, 2 H, ArH) ppm. C NMR
(125.7 MHz, CDCl ): δ = 25.1 (s, CH ), 28.8 (s, CH ), 41.2 (d, J =
31
1
s, C=N) ppm. P{ H} NMR (CD CN, 202.4 MHz): δ = 131.9 (br. s)
ppm. C H F N O PS (468.52): calcd. N 5.98, P 6.61; found N 5.97,
P 6.61.
3
3
2
3
20
32
3
2
3
31.4 Hz, C), 52.2 (s, CH ), 120.5 (s, CH), 121.7 (s, CH), 128.4 (s, CH),
2
31
1
48.3 (d, J = 99.3 Hz, CN), 149.1 (d, J = 17.6 Hz, ipso-C), ppm.
P
NMR (202.4 MHz, CDCl ): δ = 76.1 (J
= 658 Hz) ppm. MS: m/z =
3
PSe
1
-{[(Di-tert-butylphosphanyl)(phenyl)amino]methylene}piper-
+
3
99 [M + 2H] 100 %. C H N PSe (397.40): calcd. C 57.42, H 7.86,
1
9 31 2
idinium Trifluoromethanesulfonate (5f): White solid, yield 93 %,
m.p. 132–133 °C (CH CN). H NMR (300 MHz, CDCl ): δ = 1.30 [d,
1
N 7.05; found C 57.71, H 7.81, N 6.93.
3
3
J = 12.9 Hz, 20 H, C(CH ) + CH ], 1.59(m, 2 H, CH ), 1.80 (m, 2 H,
N-[Piperidin-1-yl(di-tert-butylphosphoroselenoyl)methyl-
3
3
2
2
1
CH ), 2.89 (t, J = 5.7 Hz, 2 H, CH ), 3.88 (t, J = 5.4 Hz, 2 H, CH ), 7.39 idene]aniline (7f): White crystals, yield 93 %, m.p. 107–108 °C. H
2
2
2
1
3
(
m, 5 H, ArH), 7.93 (br. s, 1 H, CH). C NMR (125.7 MHz, CDCl ): δ =
NMR (500 MHz, CDCl ): δ = 1.46–1.56 (m, 6 H, CH ), 1.51 (d, J =
3
3
2
2
4
1
2.5(s), 25.0(s), 26.3(s), 29.2 (d, J = 16.3 Hz), 36.9(d, J = 36.5 Hz),
16 Hz, 18 H, CH ), 3.09 (m, 4 H, CH ), 6.74 (d, J = 8 Hz, 2 H, CH),
3 2
1
3
8.7(s), 57.3 (s), 120.9 (q, J = 320.6 Hz, CF SO ), 126.0(s), 128.6(s), 7.04 (t, J = 7.5 Hz, 1 H, ArH), 7.31 (t, J = 7.5 Hz, 2 H, ArH) ppm.
C
3
3
3
1
30.4(s), 144.0(br. s, ipso-C), 156.2 (br. s, CH) ppm. P NMR (81 MHz,
NMR (125.7 MHz, CDCl ): δ = 23.7 (s, CH ), 26.0 (s, CH ), 28.7(s, CH ),
3 2 3 2
CDCl ): δ = 130.3 ppm. C H F N O PS (482.55): calcd. N 5.81, P
40.5 (d, J = 30.2 Hz, C), 51.6 (d, J = 1.3 Hz, CH ), 120.7 (s, CH), 123.0
3
21 34
3
2
3
2
6
.42; found N 5.96, P 6.71.
(s, CH), 128.9 (s, CH), 148.7 (d, J = 17.6 Hz, ipso-C), 156.3 (d, J =
1
7
00.6 Hz, CN), ppm. 31P NMR (81 MHz, CDCl ): δ = 76.6 (J
=
3
PSe
4
-{[(Di-tert-butylphosphanyl)(phenyl)amino]methylene}-
+
02 Hz) ppm. MS: m/z = 413 [M + 2H] 100 %. C H N PSe (411.43):
20 33 2
morpholin-4-ium Trifluoromethanesulfonate (5g): White solid,
yield 92 %, m.p. 154–156 °C (CH CN). H NMR (300 MHz, CD CN):
calcd. C 58.39, H 8.08, N 7.53; found C 58.47, H 7.96, N 7.64.
1
3
3
δ = 1.34 [d, J = 12.9 Hz, 18 H, C(CH ) ], 2.86 (m, 2 H, CH ), 3.44 (m,
N-[Morpholin-4-yl(di-tert-butylphosphoroselenoyl)methyl-
idene]aniline (7g): White crystals, yield 95 %, m.p. 126–127 °C. H
3
3
2
1
2
H, CH ), 3.83 (br. s, 4 H, 2 CH ), 7.43–7.54 (m, 5 H, HPh), 7.90 (br.
2
2
13
s, 1 H, CH) ppm. C NMR (125.7 MHz, CD CN): δ = 28.5 (d, J =
NMR (500 MHz, CDCl ): δ = 1.51 (d, J = 16 Hz, 18 H, CH ), 3.22 (m,
3
3
3
1
7.6 Hz, CH ), 36.5 (d, J = 36.5 Hz, C), 48.5 (CH ), 54.9 (CH ), 64.7
4 H, CH ), 3.68 (m, 4 H, CH ), 6.74 (d, J = 7.5 Hz, 2 H, CH), 7.05 (t,
J = 7.5 Hz, 1 H, CH), 7.31 (t, J = 7.8 Hz, 2 H, ArH) ppm. C NMR
3
2
2
2 2
1
3
(CH ), 66.15 (CH ), 121.2 (q, J = 320.6 Hz, CF ), 126.5 (CH), 128.95
2
2
3
Eur. J. Inorg. Chem. 0000, 0–0
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9
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
(
(
(
125.7 MHz, CDCl ): δ = 28.6 (s, CH ), 40.54 (d, J = 30.2 Hz, C), 50.6
precipitate was filtered off, washed with hexane (2 × 10 mL), then
hexane was removed under vacuum. The residue obtained was pu-
rified by silica gel plate chromatography (eluting with hexane: di-
chloromethane 1:1) to afford phosphane selenide 7a as yellow
3
3
s, CH ), 67.0 (s, CH ), 120.5 (s, CH), 121.7 (s, CH), 123.6 (s, CH), 129.1
2
2
s, CH), 148.1 (d, J = 16.3 Hz, ipso-C), 155.0 (d, J = 99 Hz, CN),
31
ppm. P NMR (202.4 MHz, CDCl ): δ = 77.3 (J
= 704 Hz) ppm.
3
PSe
C H N OPSe (413.40): calcd. C 55.20, H 7.56, N 6.78; found C 55.11,
rhombus solid (610 mg, 27 % m.p. 127–128 °C), R 0.5÷0.7 and com-
19
31
2
f
H 7.91, N 6.96.
pound 10 (1.57 g, 58 %; m.p. 97–98 °C, as light yellow needles) Rf
0
.3÷0.4.
Compound 10: H NMR (300 MHz, CDCl
), 6.80 (d, J = 7.5 Hz, 2 H, CHPh), 6.98
Synthesis of Compound 8a by Catalysis: To a solution of 5a
(
1
1.84 g, 4.1 mmol) in THF (20 mL) at –95 °C a solution of lithium
hexamethyldisilazide (700 mg, 4.2 mmol) in THF (10 mL) was added 18 H, tBu), 3.22 (s, 6 H, NCH
with stirring over 1 min. In 30 min a solution of 7a (320 mg, 20 mol-
(t, J = 7.5 Hz, 1 H, CHPh), 7.20 (t, J = 7.5 Hz, 2 H, CHPh), ppm.
) in THF (5 mL) was added. The reaction mixture was slowly
3
NMR (125 MHz, CDCl ): δ = 28.66 (d, J = 2.5 Hz, CH ), 42.0 (s, CH ),
): δ = 1.27 (d, J = 17.7 Hz,
3
3
1
3
C
%
3
3
warmed to –4 °C over 7 h and the stirring was kept overnight. The
solvent was evaporated to dryness and the residue was extracted
with pentane (15 mL), the undissolved precipitate was filtered off
under argon, washed with pentane (3 × 10 mL). The pentane ex-
tracts were combined, pentane was removed under vacuum. The
residue was distilled and the first fraction was collected (b.p. 90 °C/
44.46 (d, J = 22.6 Hz, C), 122.5 (s, CH), 123.6 (s, CH), 128.1 (s, CH),
143.5 (d, J = 5.0 Hz, C=N), 149.6 (s, ipso-C), ppm. 31P{ H} NMR
1
(202 MHz, CDCl
PSe (450.32): calcd. N 6.22, P 6.88; found N 6.46, P 6.98.
): δ = 117.3 (d, JPSe = 763, JP–Se = 364 Hz), ppm.
3
C
H
29
N
2
17
2
Compound 11: To a solution of 10 (320 mg, 0.7 mmol) in benzene
2.5 mL) was added tris(morpholino)phosphane (120 mg,
.74 mmol). The reaction mixture became colorless. The solvent was
(
0
0
.05 Torr) to give 1.2 g of crude 8a that was recrystallized from
pentane (1.5 g) to give 8a.
evaporated under vacuum and the residue was extracted with pent-
ane (1.5 mL), The solution was kept at –18 °C to precipitate tris-
1
,1-Di-tert-butyl-N,N-dimethyl-N′-(phenyl)phosphanylcarbox-
(morpholino)phosphine selenide which was filtered off. The filtrate
imidamide (8a): White crystals, yield 82 %, m.p. 46–47 °C (pentane).
1
was concentrated under vacuum and the residue was distilled (b.p.
1
(500 MHz, C D ): δ = 1.11 (d, J = 11.5 Hz, 18 H, tBu), 3.00 (s, 6 H,
NCH ), 6.96 (t, J = 7.5 Hz, 1 H, CH ), 7.04 (d, J = 7.5 Hz, 2 H, CHPh),
H NMR (300 MHz, CDCl ): δ = 1.28 (d, J = 12 Hz, 18 H, CH ), 2.79
3
3
1
25 °C/ 0.05 Torr) to give 11 as colorless oil (220 mg, 59 %). H NMR
(
s, 6 H, CH ), 6.70 (d, J = 7.8 Hz, 2 H, CH), 6.84 (t, J = 7.5 Hz, 1 H,
3
3
1
CH), 7.20 (t, J = 7.8 Hz, 2 H, ArH) ppm. P NMR (81 MHz, CDCl3):
δ = 28.4 ppm. C H N P (292.40): calcd. C 69.83, H 10.00, N 9.58;
6 6
3
Ph
17 29 2
13
7
3
.23 (t, J = 7.5 Hz, 2 H, CHPh), ppm. C NMR (125 MHz, C D ): δ =
0.05 (d, J = 15.1 Hz, CH ), 35.3 (d, J = 37.7 Hz, C), 41.2 (d, J = 5.0 Hz,
found C 69.63, H 10.21, N 9.68.
6 6
3
N-[piperidin-1-yl (di-tert-butylphosphanyl)methylidene]aniline
CH ), 122.6 (s, CH), 123.2 (s, CH), 128.7 (s, CH), 149.6 (d, J = 8.8 Hz,
C=N), 152.1 (s, ipso-C), ppm. P{ H} NMR (202 MHz, C D ): δ = 95.4
(d, JPSe = 216 Hz), ppm. C H N PSe (371.36): calcd. N 7.54, P 8.34;
17 29 2
found N 7.74, P 8.61.
3
1
(
8f): White crystals, m.p. 69–70 °C, H NMR (300 MHz, CDCl ): δ =
31
1
3
6 6
1
.30 (d, J = 12 Hz, 18 H, CH ), 1.40–1.49 (m, 6 H, CH ), 3.19 (m, 4 H,
3
2
CH ), 6.69 (dd, J = 8.4, J = 1.2 Hz,2 H, CH), 6.86 (t, J = 7.4 Hz, 1 H,
2
1
2
1
3
CH), 7.22 (t, J = 7.8 Hz, 2 H, ArH) ppm. C NMR (125.7 MHz, CDCl3):
δ = 24.3 (CH ), 25.9 (CH ), 30.1 (d, J = 13.8 Hz, CH ), 33.1 (d, J =
1
-(Di-tert-butylphosphanyl)-3-methyl-1,2,3,4-tetrahydroquinaz-
2
2
3
oline (12a): To a solution of 5a (2.35 g, 5.3 mmol) in THF (20 mL)
at –90 °C a solution of lithium hexamethyldisilazide (890 mg,
2
1
1.4 Hz, C), 50.4 (d, J = 15.1 Hz, CH ), 120.1 (s, CH), 120.6 (s, CH),
2
31
28.7 (s, CH), 152.1 (s, ipso-C), 163.3 (d, J = 8.8 Hz, CN), ppm.
P
5.3 mmol) in THF (15 mL) was added with stirring over 10 min. The
NMR (81 MHz, CDCl ): δ = 28.9 ppm. C H N P (332.46): calcd. C
3
20 33 2
temperature was raised to –70 °C over 2 h. The reaction mixture
was kept whilst stirring overnight at 0 °C and then the mixture was
stirred at 25 °C for 4 h. The solvent was evaporated to dryness and
the residue was extracted with pentane (30 mL), the undissolved
7
3
2.25, H 10.00, N 8.43; found C 72.43, H 10.18, N 8.20. EI-MS: m/z =
33.3 [M + 1] (96.7 %).
+
N-[Morpholin-4-yl(di-tert-butylphosphanyl)methylidene]aniline
(
8g): To a solution of tris(morpholino)phosphane (390 mg, precipitate was filtered off, washed with pentane (3 × 10 mL), the
1
.35 mmol) in C H (6 mL) a solution of 7g (560 mg, 1.35 mmol) in
pentane was removed under vacuum and the residue was distilled
(b.p. 110–112 °C/0.05 Torr) to give 12a 1.09 g (70 %) as an yellow
oil, m.p. 58–59 °C (pentane, at –18 °C). H NMR (300 MHz, C D ):
6
6
benzene (3 mL) was added and the mixture was stirred for 10–
1
15 min. The solvent was evaporated and the residue was dissolved
6
6
in pentane. The solid precipitated at –18 °C was separated by filtra- δ = 1.24 (d, J = 12.3 Hz, 18 H, tBu), 2.04 (s, 3 H, CH ), 3.45 (s, 2 H,
3
tion. The filtrate was concentrated under vacuum and the residue CH ), 3.86 (s, 2 H, CH ), 6.73–6.82 (m, 2 H, CH ), 7.10 (m, 1 H, CHPh),
2
2
Ph
13
was distilled (b.p. 130 °C/0.05 Torr) to give 8g 430 mg (96 %) as 8.03 (dd, 1 H, J = 7.2, J = 7.8 Hz, CHPh), ppm. C NMR (125.7 MHz,
1
2
1
colorless oil. H NMR (300 MHz, C D ): δ = 1.35 (d, J = 12 Hz, 18 H, C D ): δ = 29.7 (d, J = 17.6 Hz, CH ), 35.9 (d, J = 28.9 Hz, C), 41.9
6
6
6
6
3
CH ), 3.11–3.14 (m, 4 H, CH ), 3.20 (t, 4 H, J = 4.5 Hz, CH ), 6.74 (d, (CH ), 57.1 (CH ), 71.07 (d, J = 10.0 Hz, CH ), 118.65 (d, J = 31.4 Hz,
3
2
2
3
2
2
J = 7.5 Hz, 2 H, CH), 6.86 (t, J = 7.5 Hz, 1 H, CH), 7.16 (dd, J = 7.5,
CH), 118.8 (d, J = 1.3 Hz), 122.64 (d, J = 3.8 Hz, ipsoC), 126.46 (d,
J = 2.5 Hz, CH), 126.9 (CH), 147.1 (d, J = 22.6 Hz, ipsoC) ppm.
NMR (81 MHz, C D ): δ = 82.1 ppm. C H N P (292.41): calcd. C
1
3
31
J = 8.1, 2 H, ArH) ppm. C NMR (125.7 MHz, CDCl ): δ = 30.0 (d,
P
3
J = 15.1 Hz, CH ), 33.0 (d, J = 21.4 Hz, C), 49.7 (CH ), 49.8 (CH ), 66.1
3
2
2
6
6
17 29 2
(
1
2
CH ), 120.0 (s, CH), 121.1 (s, CH), 128.8 (s, CH), 151.6 (s, ipso-C), 69.83, H 10.0, N 9.58; found C 69.58, H 9.84, N 9.63.
2
3
1
62.4 (d, J = 12.6 Hz, CN), ppm. P NMR (81 MHz, C D ): δ =
6.5 ppm. C H N OP (334.44): calcd. C 68.24, H 9.34, N 8.38; found
6 6
1
-(Di-tert-butylphosphanyl)-3,6-dimethyl-1,2,3,4-Tetrahydro-
quinazoline (12b): To a solution of 5b (1.97 g, 4.3 mmol) in THF
15 mL) at –95 °C a solution of lithium hexamethyldisilazide
19 31 2
C 68.61, H 9.76, N 8.46.
(
Reactions of Carbene 9a with Selenium: To a suspension of 5a
(730 mg, 4.3 mmol) in THF (15 mL) was added with stirring over
5 min. The reaction mixture was kept whilst stirring overnight until
the temperature got slowly raised to 25 °C. The solvent was evapo-
rated to dryness and the residue was extracted with pentane
(30 mL), the undissolved precipitate was filtered, washed with pent-
ane (3 × 10 mL), the pentane was removed under vacuum and the
residue was distilled (b.p. 120 °C/0.05 Torr) to give a crude 12b that
(
2.65 g, 6.0 mmol) and selenium (950 mg, 12 mmol) in degassed
THF (20 mL) at –95 °C a solution of lithium hexamethyldisilazide
1.06 g, 6.3 mmol) in degassed THF (15 mL) was added with stirring
(
over 3 min. The reaction mixture was kept whilst stirring overnight
until the temperature rose to 22 °C. The solvent was evaporated
and the residue was dissolved in hexane (30 mL), the undissolved
Eur. J. Inorg. Chem. 0000, 0–0
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10
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
was crystallized from pentane (2.5 mL, at –18 °C) to give 12b as an
white solid, yield 50 % (650 mg), m.p. 61–62 °C. H NMR (500 MHz,
10 min. The temperature was kept at –70 °C for 1 h and then slowly
rose to 25 °C overnight, after that the reaction mixture was stirred
for another 20 h. The solvent was evaporated to dryness and the
residue was extracted with pentane (25 mL), undissolved precipitate
was filtered off under argon, washed with pentane (3 × 10 mL), the
extracts were combined, and pentane was removed under vacuum.
The oily residue was purified by distillation. The fraction with bp
110–140 °C/0.05 Torr was collected to give 12e as white solid, yield
1
C D ): δ = 1.26 (d, J = 12.0 Hz, 18 H, tBu), 2.07 (s, 3 H, NCH ), 2.16
6
6
3
(
s, 3 H, CH ), 3.47 (s, 2 H, CH ), 3.89 (s, 2 H, CH ), 6.61 (s, 1 H, CHPh),
3 2 2
6
.92 (d, J = 8.5 Hz, 1 H, CHPh), 8.49 (dd, 1 H, JHH = 8.4, JPH = 5.7 Hz,
CHPh) ppm. 13C NMR (125.74 MHz, C D ): δ = 20.6 (s, CH ), 30.1 (d,
6
6
3
J = 17.6 Hz, CH ), 36.3 (d, J = 28.9 Hz, C), 42.3 (CH ), 57.5 (CH ), 71.6
3
3
2
(
d, J = 10.0 Hz, CH ), 119.0 (d, J = 31.4 Hz, CH), 122.8 (d, J = 5.0 Hz,
2
1
ipsoC), 127.6 (d, J = 2.5 Hz, CH), 127.7 (CH), 145.1 (d, J = 23.9 Hz,
60 %, (530 mg), m.p. 68–70 °C (pentane). H NMR (500 MHz, C D ):
6
6
ipsoC) ppm. 3 P NMR (81 MHz, C D ): δ = 81.3 ppm. MS: m/z =
1
δ = 1.23 (d, J = 12.5 Hz, 9 H, tBu), 1.26 (d, J = 13.5 Hz, 9 H, tBu),
6
6
+
3
9
07.2 [M + 1] 100 %. C H N P (306.43): calcd. C 70.55, H 10.2, N
1.50–1.58 (m, 3 H, CH ), 2.02 (m, 1 H, CH ), 2.68 (m, 1 H, CH ), 2.78
1
8
31
2
2
2
2
.14; found C 70.36, H 10.39, N 9.03.
(m, 1 H, CH ), 3.95 (m, 1 H, CH), 4.06 (d, J = 10.0 Hz, 1 H, CH ), 4.27
2
2
(
7
d, J = 10.0 Hz, 1 H, CH ), 6.79 (t, J = 7.5 Hz, CHPh), 6.92 (d, J =
2
1
-(Di-tert-butylphosphanyl)-5-dimethylamino-3-methyl-1,2,3,4-
.0 Hz, CHPh), 7.10 (t, J = 7.5 Hz, CHPh), 8.10 (t, J = 7.5 Hz, CHPh)
Tetrahydroquinazoline (12c): To a solution of 5c (1.26 g, 2.6 mmol)
in THF (20 mL) at –90 °C a solution of lithium hexamethyldisilazide
13
ppm. C NMR (125.74 MHz, C D ): δ = 23.2 (CH ), 29.67 (d, J =
6
6
2
1
2
1
1
6.3 Hz, CH ), 30.0 (d, J = 17.6 Hz, CH ), 32.2 (CH ), 35.57 (d, J =
3 3 2
(440 mg, 2.6 mmol) in THF (20 mL) was added with stirring over
6.4 Hz, C), 36.2 (d, J = 30.2 Hz, C), 50.7 (CH ), 60.9 (CH), 66.1 (d, J =
2
1
0 min. The reaction mixture was kept whilst stirring for 1.5 h while
0.0 Hz, CH ), 118.6 (d, J = 32.7 Hz, CH), 119.1 (d, J = 2.5 Hz, CH),
2
the temperature got raised to –60 °C and a clear solution formed.
The reaction mixture was warmed with stirring for 24 h at –15 °C.
The solvent was evaporated to dryness and the residue was distilled
3
1
26.2 (d, J = 1.3 Hz, CH), 147.3 (d, J = 22.6 Hz, ipsoC) ppm. P NMR
+
(81 MHz, C D ): δ = 79.8 ppm. EI-MS 319.2–97 % [M + 1] . C H N P
6 6 19 31 2
(
8
318.45): calcd. C 71.66, H 9.81, N 8.80; found C 71.73, H 9.88, N
.97.
(b.p. 130 °C/0.05 Torr) to give a crude 12c that was crystallized from
pentane (1.5 mL, at –18 °C) to give 12c as a white solid, yield 90 %
1
5-(Di-tert-butylphosphanyl)-6,8,9,10,11,11a-hexahydro-5H-pyr-
ido[1,2-c]quinazoline (12f): To a solution of 5f (3.3 g, 6.9 mmol)
in THF (20 mL) at –78 °C a solution of lithium hexamethyldisilazide
(780 mg), m.p. 100–101 °C (pentane). H NMR (300 MHz, C D ): δ =
6 6
1
3
7
.28 (d, J = 12.6 Hz, 18 H, tBu), 2.39 (s, 3 H, CH ), 2.64 (s, 6 H, CH ),
.71 (s, 2 H, CH ), 4.04 (s, 2 H, CH ), 6.57 (d, J = 7.8 Hz, 1 H, CHPh),
. 03 (dd, 1 H, J = 8.1, J = 8.1 Hz, CH ), 7. 54 (dd, 1 H, J = 7.2,
3 3
2
2
(
1.1 g, 6.8 mmol) in THF (20 mL) was added with stirring over
1
2
3
Ph
1
1
10 min. The temperature was kept at –78 °C for 30 min, then slowly
rose to 0 °C and then the reaction mixture was stirred for 7 days.
The solvent was evaporated to dryness and the residue was ex-
tracted with pentane (30 mL), the undissolved precipitate was fil-
tered off, washed with pentane (3 × 10 mL), the extracts were com-
bined and the pentane was removed under vacuum. The oily resi-
due was distilled. The first crop gave tBu PNHPh (b.p. 60–98 °C/
0
by silica gel plate chromatography (eluting with dichloromethane)
to afford 8f, 490 mg (22 %), m.p. 69–70 °C, R 0.2–0.7 and white
J2 = 7.2 Hz, CHPh) ppm. C NMR (125.74 MHz, CDCl ): δ = 29.61 (d,
J = 17.6 Hz, CH ), 35.76 (d, J = 27.7 Hz, C), 42.23 (s, CH ), 44.51 (s,
CH ), 54.13 (CH ), 70.70 (d, J = 10.0 Hz, CH ), 109.08 (d, J = 1 Hz,
3
3
3
3
2
2
CH), 113.02 (d, J = 33.9 Hz, CH), 117.17 (d, J = 4 Hz, C), 125.8 (d, J =
Hz, CH), 147.27 (d, J = 21 Hz, ipsoC), 151.59 (d, J = 1.3 Hz, ipsoC)
4
31
ppm. P NMR (81 MHz, CDCl ): δ = 80.7 ppm. C H N P (335.48):
calcd. C 68.03, H 10.22, N 12.53; found C 68.17, H 10.45, N 12.40.
3
19 34 3
2
.05 Torr). The second crop (b.p. 150–155 °C) was further purified
5
-(Di-tert-butylphosphanyl)-2,4,5,9b-tetrahydro-1H-azeto[1,2-
c]quinazoline (12d): To a suspension of 5d (3.0 g, 6.6 mmol) in
THF (17 mL) at –90 °C a solution of lithium hexamethyldisilazide
f
solid 12f 1.05 g (46 %), m.p. 45–46 °C (pentane, –18 °C), R 0.8–1.0.
f
(
1.1 g, 6.6 mmol) in THF (15 mL) was added with stirring over
1
H NMR (500 MHz, C D ): δ = 1.21 [d, J = 12 Hz, 9 H, C(CH ) ], 1.29
6
6
3 3
1
0 min. The temperature was raised to –50 °C over 3 h. The reaction
[
1
d, J = 12.5 Hz, 9 H, C(CH ) ], 1.44 (m, 3 H), 1.50 (m, 1 H), 1.66 (m,
3 3
31
mixture was kept whilst stirring at –4 °C for 17 days until the
P
H), 1.90 (t, 1 H), 2.02 (d, 1 H), 2.65 (d, 1 H), 3.22 (d, J = 10.5 Hz, 1
signal of the carbene disappeared. Then the solvent was evaporated
to dryness. The residue was extracted with pentane (50 mL), undis-
solved precipitate was filtered off under argon, washed with pent-
ane (3 × 20 mL), pentane was removed under vacuum and the resi-
due was distilled (b.p. 150 °C/0.05 Torr) to give 12d as a white solid,
yield (54 %) 1.07 g, m.p. 74–75 °C (pentane, at –18 °C). 1H NMR
H), 3.69 (d, J = 10.5 Hz, 1 H), 4.19 (d, J = 10.5 Hz, 1 H), 6.78 (t, J =
.0 Hz, 1 H, ArH), 6.99 (d, J = 7.5 Hz, 1 H, ArH), 7.09 (t, J = 7.5 Hz, 1
7
13
H, ArH), 8.00 (t, J = 7 Hz, 1 H, ArH) ppm. C NMR (125.7 MHz, C D ):
6
6
δ = 25.1(s), 25.5(s), 29.3 (d, J = 17.6 Hz), 30.1 (d, J = 17.6 Hz), 32.0
(
(
s), 35.3 (d, J = 26.4 Hz), 36.7 (d, J = 31.4 Hz), 52.8 (s), 63.7 (s), 70.5
d, J = 10.1 Hz), 125.2 (s), 126.3 (s), 126.8 (d, J = 3.8 Hz), 147.6 (d,
(
500 MHz, CDCl ): δ = 1.26 (d, J = 12 Hz, 9 H, tBu), 1.31 (d, J =
31
3
J = 22.6 Hz) ppm. P NMR (81 MHz, C D ): δ = 82.6 ppm. C H N P
6 6 20 33 2
1
2.5 Hz, 9 H, tBu), 1.75 (t, J = 9 Hz, 1 H, CH), 2.94 (m, 1 H, CH), 3.39
(332.47): calcd. C 72.25, H 10.00, N 8.43; found C 72.42, H 10.21, N
(t, J = 7 Hz, 1 H, CH), 3.88 (m, 1 H, CH), 4.04 (d, JPH = 12.5 Hz, CH2),
8.71.
4
.44 (d, JPH = 12.5 Hz, CH ), 4.78 (d, J = 7.5 Hz, CH), 6.82 (t, J =
2 PH
N-(Di-tert-butylphosphanyl)-N-phenyl-3-vinyloxazolidin-2-
amine (13): To a solution of salt 5g (4.04 g, 8.35 mmol) in THF
7
Hz, HPh), 6.92 (d, J = 7.5 Hz, HPh), 7.11 (t, J = 8 Hz, HPh), 8.12 (t,
1
3
J = 8 Hz, HPh) ppm. C NMR (125.7 MHz, CDCl ): δ = 28.9 (CH ),
3
2
(22 mL) at –70 °C a solution of lithium hexamethyldisilazide (1.4 g,
2
2
8
1
3
9.8 (d, J = 17.6 Hz, CH), 30.5 (d, J = 16.3 Hz, CH), 35.3 (d, J =
8.33 mmol) in THF (10 mL) was added with stirring over 10 min.
6.4 Hz, C), 36.5 (d, J = 30.2 Hz, C), 46.6 (CH ), 59.5(CH), 64.3 (d, J =
2
The reaction mixture was stirred at –60 °C for 30 min and then it
was warmed over 24 h to room temp. Then the solvent was evapo-
rated and the residue was extracted with pentane (25 mL), the un-
dissolved precipitate was separated by decantation and the solution
was evaporated under vacuum to give light-yellow viscous oil. It
was distilled (b.p. 120 °C/0.05 Torr) to give 13 1.11 g (40 %) as a
.8 Hz, CH ), 117.9 (d, J = 40.2 Hz, CH), 119.4 (d, J = 1.3 Hz, CH),
2
26.0 (d, J = 3.8 Hz, CH), 127.4 (d, J = 1.3 Hz, CH), 127.8 (d, J =
3
1
1
.8 Hz, CH ), 147.8 (d, J = 22.6 Hz, CH ) ppm. P{ H} NMR (202 MHz,
2
2
CDCl ): δ = 71.4 ppm. C H N P (304.42): calcd. C 71.02, H 9.60, N
3
18 29 2
9
.20; found C 70.87, H 9.75, N 9.11.
1
6
-(Di-tert-butylphosphanyl)-1,2,3,5,6,10b-hexahydropyrrolo-
colourless solidified oil. H NMR (500 MHz, C D ): δ = 1.31 (d+br. s,
6
6
[1,2-c]quinazoline (12e): To a solution of 5e (1.3 g, 2.8 mmol) in
J = 12.0 Hz, 18 H, tBu), 2.58 (m, 2 H, CH ), 3.38 (q, 1 H, J = 26.4 Hz,
2
THF (20 mL) at –90 °C a solution of lithium hexamethyldisilazide
1/2CH ), 3.50 (br. s, 1 H, 1/2CH ), 3.66 (br. d, J = 26.4 Hz, 1 H,
2
2
(
490 mg, 2.9 mmol) in THF (20 mL) was added with stirring over 1/2CH=CH ), 3.94 (br. d, J = 26.4 Hz, 1 H, 1/2CH=CH ), 6.13 (s, 1 H,
2
2
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*
CH), 6.71 (dd, 1 H, J = 15.5, J = 12.2 Hz, CH=CH ), 6.935 (t, J =
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.0/7.5 Hz, 1 H, CHPh), 7.09 (m, 2 H, CHPh), 7.515 (d, J = 7.0 Hz, 2 H,
CHPh) ppm. 1 C NMR (125.7 MHz, C D ): δ = 29.75 (d, J = 17.6 Hz,
3
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6
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(br. s, CH ), 83.0 (CH ), 124.9 (br. s, CH), 128.0 (CH), 130.2 (br. s,
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6
6
19
31
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The first crop gave tBu PNHPh (b.p. 90 –120 °C/0.05 Torr). The sec-
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(pentane, –18 °C) to give 8f (0.41 g, 54 %).
Acknowledgments
MCIA (Mésocentre de Calcul Intensif Aquitain) and IPREM are
gratefully acknowledged for calculation facilities.
Keywords: Carbenes · Phosphanes · Azomethine ylides ·
Cyclization · Nitrogen heterocycles
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Received: September 19, 2018
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Full Paper
Carbene Cyclization
In the absence of a trapping agent PIII-
N-substituted acyclic diaminocarbenes
prepared by deprotonation of the cor-
responding salts isomerize into tran-
sient azomethine ylides followed by
electrophilic aromatic substitution to
A. Marchenko, G. Koidan,
A. Hurieva, Y. Vlasenko, A. B. Rozhenko,*
J.-M. Sotiropoulos, A. Kostyuk* ... 1–13
V
Transformation Routes of P - and
III
P -N-Substituted Acyclic Diamino-
V
afford tetrahydroquinazolines. P -N-
carbenes
substituted acyclic diaminocarbenes
undergo 1,2-phosphorus shift result-
ing in phosphane selenides.
DOI: 10.1002/ejic.201801141
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim