Palladium-catalyzed decarbonylative rearrangement of N-Allenyl seleno- and tellurocarbamates

Article abstract of DOI:10.1002/hc.21217

Decarbonylative rearrangement of seleno- and tellurocarbamates carrying an allenyl group on the nitrogen was found to proceed in the presence of a palladium catalyst to afford 3-chalcogeno-1-azadienes. This transformation may involve oxidative addition of

Full text of DOI:10.1002/hc.21217

Heteroatom Chemistry
Volume 25, Number 6, 2014
Palladium-Catalyzed Decarbonylative
Rearrangement of N-Allenyl Seleno- and
Tellurocarbamates
Daisuke Shiro,1 Hiroyuki Nagai,1 Shin-ichi Fujiwara,2
Susumu Tsuda,2 Takanori Iwasaki,1 Hitoshi Kuniyasu,1
and Nobuaki Kambe1
1Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Osaka
565-0871, Japan
2Department of Chemistry, Osaka Dental University, Osaka 573-1121, Japan
Received 11 February 2014; revised 3 July 2014
comitantly with carbon–heteroatom bond forma-
ABSTRACT: Decarbonylative rearrangement of
tion. A promising approach to achieve this trans-
seleno- and tellurocarbamates carrying an allenyl
formation is the insertion of an unsaturated car-
group on the nitrogen was found to proceed in the pres-
bon unit over a carbon–heteroatom bond. This
ence of a palladium catalyst to afford 3-chalcogeno-
type of transformation has been extensively ex-
1-azadienes. This transformation may involve oxida-
plored using transition metal catalysts [2]. For ex-
tive addition of Pd to a carbon–chalcogen bond,
ample, we have reported that carbamoselenoates 1
decarbonylation from a carbamoylpalladium unit
having a terminal alkynyl moiety on the nitrogen
(R2N-C(O)-PdChPh: Ch = Se or Te), Pd shift, and
atom underwent selenocarbamoylation of alkynes
ꢀC
reductive elimination.
2014 Wiley Periodicals,
intramolecularly with high regio- and stereoselec-
tivities to afford four- to eight-membered lactams
2 having an exocyclic double bond in high yields
by the use of Pd(PPh3)4 as a catalyst (Eq. (1)) [3].
The treatment of vinylselenides 3 having a alkynyl-
methyl group on the nitrogen atom with Pt(PPh3)4
afforded six-membered lactam frameworks 4 or
5 having a dienone unit by cis-vinylselenation of
alkynes (Eq. (2)) [4]. We also demonstrated Pd(0)-
catalyzed selenocarbamoylation of allene, where
carbamoselenoates 6 with a terminal allenyl group
on the nitrogen atom afforded the corresponding
α,β-unsaturated lactams 7 bearing an allylselenide
moiety with perfect regioselectivity (Eq. (3)) [5].
Inc. Heteroatom Chem. 25:518–524, 2014; View
this article online at wileyonlinelibrary.com. DOI
10.1002/hc.21217
INTRODUCTION
Transition metal catalyzed addition of heteroatom-
containing compounds to unsaturated hydrocar-
bons has been well exploited as one of the most
straightforward methods for the introduction of het-
eroatom functionalities to organic molecules [1].
This transformation becomes more attractive and
useful if carbon–carbon bonds can be created con-
Correspondence to: Nobuaki Kambe; e-mail: kambe@chem
.eng.osaka-u.ac.jp.
Dedicated to 77th birthday of Professor Renji Okazaki.
2014 Wiley Periodicals, Inc.
ꢀC
(1)
518

Palladium-Catalyzed Decarbonylative Rearrangement of N-Allenyl Seleno- and Tellurocarbamates 519
(2)
obtained as the major product when PPhMe2 was
employed (entry 5). To suppress decarbonylation,
the reaction was performed under pressurized car-
bon monoxide (20 atm); however, the yield of lac-
tam 11 was not improved (entry 6). The use of
electron-rich and sterically less hindered phosphine
(3)
ligands tends to favor the lactam formation. How-
ever, PCy3 gave nearly 1:1 mixture of 10a and 11,
indicating that product selectivities cannot be sim-
ply explained (entry 7). Bidentate ligands such as
1,4-Bis(diphenylphosphino)butane (dppb) and 1,2-
Bis(diphenylphosphino)ethane (dppe) afforded only
azadiene 10a like PPh3 (entry 1) in a similar manner
with a lower yields, respectively (entries 1, 9, 10).
Both 1,5-Bis(diphenylphosphino)pentane (dppen)
and 1,6-Bis(diphenylphosphino)hexane (dpphex)
gave a mixture of 10a and 11 with nearly 3:1 and 2:1
ratio, respectively, as in the case of PPh2Me probably
due to the flexible tether chains (entries 4, 11, 12).
On the contrary, when 2,2ꢁ-Bis(diphenylphosphino)-
1,1ꢁ-binaphthalene (BINAP) was employed, 3-seleno-
1-azadiene 10a was obtained in 88% yield (entry
13). Although it is unclear yet why BINAP can pro-
mote this reaction efficiently, the formation of by-
products was largely suppressed. From the results
in entries 9–14, the yields of azadiene 10a do not
In this paper, we examined the reaction of
seleno- and tellurocarbamate 8 possessing an allenyl
group on the nitrogen atom and unexpectedly found
that the decarbonylative rearrangement occurred,
giving rise to 1-azadienes 10 without the formation
of a four-membered lactam 9 (Eq. (4)).
(4)
RESULTS AND DISCUSSION
At first, we conducted the reaction of 8 under sim-
ilar conditions as employed in Eq. (3). Thus, when
a toluene solution containing selenocarbamate 8a
and Pd(PPh3)4 (5 mol%) was heated at 80°C for
5 h, 1-azadiene 10a was obtained in 36% yield
(Table 1, entry 1). Ni(cod)2 and Pt(PPh3)4 were also
effective as a catalyst albeit in lower yields (entries 2
and 3). The use of aprotic and polar solvents such as
CH3CN, dimethylformamide (DMF), and dimethyl
sulfoxide (DMSO) afforded the product in better
yields. Among them, DMF gave the best yield of 58%
(entries 4–8). In all entries, diphenyl diselenide and
several unidentified compounds were detected as by-
products.
In Table 2, results obtained using monodentate
and bidentate phosphine ligands were summarized.
Triarylphosphines-bearing electron-donating or -
withdrawing groups afforded similar results (entries
1–3). Monodentate alkyl phosphines and phosphites
were not effective for the synthesis of 1-azadiene
10a (entries 4–8). Interestingly, a four-membered
lactam 11, not incorporating selenium, was
TABLE 1 Reaction of 8a with Group 10 Metal Complexes in
Various Solvents
Entry
Catalyst
Solvent Conversion (%)a Yield (%)a
1
2
3
4
5
6
7
8
Pd(PPh3)4 Toluene
Ni(cod)2 Toluene
77
>95
17
>95
>95
92
36
28
<5
53
58
52
33
20
Pt(PPh3)4 Toluene
Pd(PPh3)4 CH3CN
Pd(PPh3)4 DMF
Pd(PPh3)4 DMSO
Pd(PPh3)4 Dioxane
Pd(PPh3)4 EtOH
63
77
a1H NMR yield.
Heteroatom Chemistry DOI 10.1002/hc

520 Shiro et al.
TABLE 2 Pd-Catalyzed Rearrangement of 8a Using Various
Ligands
FIGURE 1 DFT Calculations.
Entry
Ligand
PPh3
P(C6H4-p-MeO)3 10
P(C6H4-p-CF3)3 10
PPh2Me
PPhMe2
PPhMe2
PCy3
X
10a (%)a 11 (%)a Angleb
unfortunately. Another possible pathway via inter-
mediate 9 formed by intramolecular cyclization of A
may not likely because deselenation did not proceed
when the similar α,β-unsaturated lactams 7 bearing
an allylselenide moiety were treated with Pd(PPh3)4
[ [5]a]. The formation of π-allylpalladium intermedi-
ate F’ from A leading to F via reductive deselenation
cannot be ruled out.
1
2
3
4
10
47
53
51
23
<5
6
17
48
26
–
5
–
12
30
36
15
–
145
145
145
136
122
122
170
109
86
10
10
10
10
10
5
5
5
5
5
5
6c
7
8
9
10
11
12
13
14
P(OEt)3
dpped
–
dppbe
45
–
94
DFT calculations [8] were performed to get infor-
mation on the rearrangement pathways. These cal-
culations were carried out using the Gaussian 09W
set of programs with the B3LYP functional, the 6-
31+G(d) basis set for all nonmetallic atoms (H, C,
O, N, P), and the LANL2DZ basis set for Pd and
Se. In Fig. 1, Bꢀ, Cꢀ, and Dꢀ are the model com-
pounds for possible intermediates B, C, and D in
Scheme 1. Although aza-π-allylpalladium complex
Cꢀ was not optimized as a stable structure, com-
plex Dꢀ was found to be 19.2 kcal/mol more sta-
ble than complex Bꢀ. This result may reflect the
difference of bond dissociation energies between
dpppenf
dpphexg
rac–BINAPh
DPEphos
51
19
88 (79)
18
12
–
93
104
5
61
–
a1H NMR yield (isolated yield).
bCone angles (entry 1–8) and bite angles (entry 9–14).
cThe reaction was carried out under 20 atm CO.
d 1,2-Bis(diphenylphosphino)ethane.
e1,4-Bis(diphenylphosphino)butane.
f1,5-Bis(diphenylphosphino)pentane.
g1,6-Bis(diphenylphosphino)hexane.
h2,2ꢁ-Bis(diphenylphosphino)-1,1ꢁ-binaphthalene.
C
Pd and N Pd bonds [9]. Although the bond dis-
seem to have simple correlation with bite angles of
bidentate phosphines [6].
sociation energy of the N Pd bond is unknown,
the C Pt bond is about 49 kcal/mol more stable
than the N Pt bond. From these results, we propose
that the relative stability of Dꢀ over Bꢀ would be the
driving force of decarbonylation and rearrangement,
and the rearrangement from Bꢀ to Dꢀ may proceed
through an aza-π-allylpalladium complex Cꢀ.
Next, carbamoselenoate 8b bearing a benzyl
group on the nitrogen was employed as a substrate.
When 8b was treated under similar reaction con-
ditions, a decarbonylative rearrangement also pro-
ceeded giving rise to 3-seleno-1-azadiene 10b in 47%
Plausible reaction pathways for the formation
of 1-azadiene 10 and lactam 11 are depicted in
Scheme 1. In the formation of 1-azadiene 10a (right-
hand side), the first step would be oxidative ad-
dition of the carbamoyl carbon–selenium bond of
selenocarbamate 8a to palladium to generate a
NC(O) Pd Se unit affording intermediate A. Since
no methylene chain exists between the nitrogen
atom and the allenyl group in A, coordination of
the terminal double bond of the allenyl group to pal-
ladium is sterically difficult. Thus decarbonylation
may occur to give intermediate B. Azadien 10a may
be obtained by reductive elimination of D, generated
from B via aza-π-allylpalladium intermediate C. The
formation of aza-π-allylpalladium is suggested in the
literature [7].
As for the formation of the lactam 11 (left-hand
side), the SePh group of oxidative adduct A would be
replaced with the hydrogen atom leading to E. The
Allen part of E then undergoes carbo- or hydropal-
ladation giving F or G, and the following reductive
elimination would afford lactam 11. Although the
formation of diphenyl diselenide was confirmed, all
our attempts to identify the hydrogen source failed
1
yield (Eq. (5)). H NMR of the crude mixture of the
reaction using a selenocarbamate having a phenyl
group on the nitrogen suggested that the correspond-
ing 1-azadiene was formed in 37%; however, isola-
tion of this product was not successful because it
was hydrolyzed during purification.
(5)
Heteroatom Chemistry DOI 10.1002/hc

Palladium-Catalyzed Decarbonylative Rearrangement of N-Allenyl Seleno- and Tellurocarbamates 521
In addition, this transformation also proceeded
adducts having the R C(O) M structure [11]. To
the best of our knowledge, decarbonylation from the
carbamoyl–metal unit (R2N C(O) M) has never
been reported.
when a tellurium analogue was used (Eq. (6)). The
corresponding 1-azadiene 10c was obtained in 49%
yield from tellurocarbamate 8C.
In summary, we found that the decarbonylative
rearrangement proceeded by the treatment of an
N-allenyl seleno- and tellurocarbamates 8 with the
palladium catalyst to give a 3-seleno or 3-telluro-1-
azadiene 10, in which the use of rac-BINAP as a lig-
and afforded the highest yield. This transformation
involves unusual decarbonylation from carbamoyl-
Pd units. In addition, a four-membered lactam 11
incorporating no chalcogen atom was obtained as a
major product in moderate yields by using PPhMe2
as the ligand.
(6)
When 1-azadiene 10a was allowed to react with
CO (20 atm) in the presence of Pd(PPh3)4, 10a was
remained unchanged (Eq. (7)). This result indicates
that the reverse process does not exist in this trans-
formation.
EXPERIMENTAL
General
1H NMR and 13C NMR spectra were recorded with
a JEOL JNM-Alice 400 (400 and 100 MHz, re-
spectively) spectrometer using CDCl3 as solvents
and using Me4Si as an internal standard. Chem-
ical shifts were reported in parts per million (δ)
downfield from internal tetramethylsilane. Data are
reported as follows: chemical shift in ppm (δ),
multiplicity (s = singlet, d = doublet, t = triplet,
br = broad singlet, m = multiplet, c = com-
plex), coupling constant (Hz), integration. Infrared
spectra (IR) were obtained on a JASCO Corpo-
ration FT/IR-4200 instrument equipped with ATR
(7)
Decarbonylation is frequently encountered in
transition metal mediated reactions of carbonyl
compounds. This decarbonylation usually oc-
curs from intermediates having a structure of
R
C(O) M, generated by oxidative addition of acid
halides, aldehydes, etc. [10]. Transition metal cat-
alyzed decarbonylation of esters, thioesters, acyl-
stannanes, and phthalimides has also reported been
and is considered to proceed through oxidative
SCHEME 1 A plausible reaction pathway.
Heteroatom Chemistry DOI 10.1002/hc

522 Shiro et al.
PRO450-S. Infrared spectra were recorded with a
JASCO Corporation FT/IR-4200 instrument. Both
conventional and high-resolution mass spectra were
recorded with a JEOL JMS-DX303HF spectrom-
eter (EI) or JEOL JMS-T100TD (DART). HPLC
separations were performed on a recycling prepar-
ative HPLC (Japan Analytical; Model LC-908)
equipped with JAIGEL-1H and -2H columns (GPC)
using CHCl3 as an eluent. 1-Phenethylamine,
diphenyl diselenide (Sigma-Aldrich, Tokyo, Japan),
diphenyl ditelluride, propargyl bromide, triphosgen
(Tokyo Chemical, Tokyo, Japan), pyridine, sodium
borohydride (Kishida Chemical, Osaka, Japan),
potassium tert-butoxide (Nacalai Tesque, Kyoto,
Japan), and dehydrated solvents (Wako Pure Chem-
ical, Osaka, Japan) were purchased and used as re-
ceived.
(24.6 mmol) was then added dropwise in
CH2Cl2 (60 mL) from the funnel. After the mix-
ture was warmed up to room temperature, the
stirring was continued overnight. After the mix-
ture was poured into HCl (1 M) and extracted
with CH2Cl2 (50 mL × 2), the combined or-
ganic phase was dried with MgSO4. The solvents
were removed in vacuo, and the black product
was used in the next process without purifica-
tion. Caution: Triphosgen decomposes slightly
to generate highly poisonous phosgene in air.
All operation should be carried out in a well-
ventilated hood.
iii. A-300 mL three-necked flask with a magnetic
stirrer and a 50-mL dropping funnel were dried
with the heat gun at 120°C and then purged with
N2. Into a 300-mL flask, diphenyl diselenide
(5.5 mmol), sodium borohydride (30 mmol),
and THF (50 mL) were placed under N2 and the
suspension was cooled to 0°C. After methanol
(4 mL) was added slowly, vigorous bubbling
was occurred. After the color changed from pale
yellow to white (about 30 min), N-phenethyl-
N-prop-2-ynylcarbamoyl chloride (10 mmol) in
THF (60 mL) was added at the room tem-
perature, and the mixture was stirred for
3 h. After the mixture was poured into brine
(50 mL) and extracted with Et2O (50 mL × 2),
the combined organic phase was dried with
MgSO4. The solvents were removed in vacuo,
and the residue was purified by silica gel col-
umn chromatography (n-hexane/Et2O = 2/1,
Rf = 0.5) to afford Se-phenyl N-phenethyl-N-
propa-2-ynylcarbamoselenoate (83%).
Synthesis of Selenocarbamate 8a.
i. A-30 mL three-necked flask with a magnetic stir-
rer and a 100-mL dropping funnel were dried
with a heat gun at 120°C and then purged
with N2. After cooling to room temperature,
1-phenethylamine (120 mmol) was placed in
the flask, 1-propargyl bromide (30 mmol) was
added in the dropping funnel, and the flask was
cooled in an ice bath. The solution in the funnel
was added into the flask dropwise, and the re-
action mixture was stirred overnight at room
temperature. After the mixture was poured
into NaOH (1 M) and extracted with Et2O
(30 mL × 2), the combined organic phase
was dried with MgSO4. The solvents were re-
moved in vacuo, and the residue was purified by
silica gel column chromatography (n-hexane/
EtOAc = 4/3, Rf = 0.3) to afford N-phenethyl-
N-propa-2-ynylamine (82%).
ii. A-200 mL three-necked flask with a mag-
netic stirrer and a 100-mL dropping funnel
were dried with the heat gun at 120°C and
then purged with N2. Into a flask, triphosgen
(12.3 mmol) and CH2Cl2 (60 mL) were placed
under N2. After cooling in an ice bath, pyri-
dine (24.6 mmol) was added carefully. To
the solution, N-phenethyl-N-prop-2-ynylamine
iv. A-50 mL two-necked flask with a magnetic
stirrer was dried with the heat gun at
120°C and then purged with N2. Into a 50-
mL flask, Se-phenyl N-phenethyl-N-propa-2-
ynyl carbamoselenoate (8.29 mmol) and THF
(50 mL) were placed and the suspension was
cooled to –42°C (CH3CN/dry ice bath). Into
the flask, potassium tert-butoxide (1.66 mmol)
was added at the same temperature and the
mixture was stirred for 3 h. After the potas-
sium tert-butoxide was filtered with celite and
Et2O, the mixture was poured into brine
(30 mL) and extracted with Et2O (30 mL ×
2), the combined organic phase was dried
with MgSO4. The solvents were removed in
vacuo, and the residue was purified by GPC
to afford Se-phenyl N-phenethyl-N-propa-1,2-
1
dien-1-ylcarbamoselenoate 8a (60%): H-NMR
(400 MHz, CDCl3): δ = 2.94 (td, J = 7.5 Hz, J =
26.8 Hz, 2H), 3.68 (td, J = 7.8 Hz, J = 14.4 Hz,
2H), 5.47 (dd, J = 6.0 Hz, J = 12.9 Hz, 2H), 6.65
Heteroatom Chemistry DOI 10.1002/hc

Palladium-Catalyzed Decarbonylative Rearrangement of N-Allenyl Seleno- and Tellurocarbamates 523
5.33 (d, J = 17.2 Hz, 2H), 6.64 (s, 1H), 7.25–7.45 (m,
(s, 1H), 7.19–7.59 (m, 10H) ppm. 13C NMR (100
8H), 7.57–7.65 (m, 2H), ppm. 13C NMR (100 MHz,
CDCl3): δ 50.2, 50.4, 87.2, 88.3, 99.5, 99.7, 126.7,
127.5, 128.1, 128.4, 128.6, 128.8, 129.2, 129.5, 129.9,
135.6, 136.0, 136.7 (JSe-C = 5.3 Hz), 136.7, 163.9,
164.2, 202.3, 202.9 ppm. IR (NaCl) 3059, 2373, 2323,
1955, 1667 (C O), 1578, 1496, 1475, 1439, 1378,
1295, 1251, 1173, 1098, 1073, 1022, 960, 878, 737,
688 cm–1; MS (EI) m/z (relative intensity, %) 329
(M+, 2), 301 (5), 238 (2), 220 (14), 172 (4), 157 (5),
91 (100). Anal. HRMS (EI) calcd for C17H15NOSe:
329.0319, Found . 329.0320.
MHz, CDCl3): δ 33.7, 34.5, 48.8, 87.0, 87.9, 98.9,
99.7, 125.9, 128.4, 128.6, 128.8, 129.1, 136.6
(JSe-C = 5.8 Hz), 137.9, 138.4, 163.1, 202.0 ppm.
IR (NaCl) 3037, 2968, 2939, 2359, 1955, 1713,
1670 (C O), 1441, 1382, 1257, 1245, 1139, 1001,
874, 732, 694, 687, 672, 607, 561 cm−1; MS (EI)
m/z (relative intensity, %) 343 (M+, 5), 315 (8),
234 (34), 224 (9), 186 (6), 157 (14), 130 (7), 105
(100); Anal. Calcd for C18H17NOSe: C, 63.16; H,
5.01; N, 4.09, Found C, 62.98; H, 4.83; N, 4.15.
Pd(dba)2/rac-BINAP-Catalyzed
Decarbonyla-
(E)-N-benzyl-2-(phenylselanyl)prop-2-en-1-imine
10b. 1H NMR (400 MHz, CDCl3): δ = 4.80 (s,
2H), 5.27 (s, 1H), 5.97 (s, 1H), 7.24–7.44 (m, 8H),
7.60–7.69 (m, 2H), 8.05 (s, 1H) ppm. 13C NMR (100
MHz, CDCl3): δ 63.6, 122.2, 126.7, 127.0, 127.9,
128.5, 128.6, 128.8, 129.5, 137.2 (JSe-C = 5.3 Hz),
138.7, 143.8, 161.5 ppm. IR (NaCl) 3059, 3028,
2848, 1953, 1632 (C N), 1584, 1494, 1475, 1452,
1437, 1346, 1301, 1230, 1156, 1065, 1022, 999, 960,
889, 845, 819, 736, 692 cm–1; MS (EI) m/z (relative
intensity, %) 301 (M+, 21), 220 (92), 183 (4), 157
(6), 144 (14), 130 (23), 104 (18), 91 (100); Anal.
HRMS (EI) calcd for C16H15NSe: 301.0370, Found.
301.0371.
tive Isomerization of 8a. A 5-mL reaction flask
equipped with a reflux condenser was dried with
the heat gun at 120°C and then purged with N2.
After cooling to room temperature, Pd(dba)2 (0.02
mmol), rac-BINAP (0.02 mmol), DMF (1.0 mL),
and 8a (0.4 mmol) were placed in the flask and
added to the resulting black solution. The reaction
mixture was heated in an oil bath at 80°C for 5 h.
After cooling to room temperature, the volatiles
were removed in vacuo. After the yield of 1-azadiene
10a was determined by 1H NMR spectroscopy
with 3-pentanone as an internal standard, 10a was
purified with GPC (79%).
(E)-N-Phenetyhyl-2-(phenylselanyl)prop-2-en-1-
imine 10a. 1H NMR (400 MHz, CDCl3): δ = 2.98 (t,
J= 7.6 Hz, 2H), 3.80 (t, J = 7.6 Hz, 2H), 5.21 (s, 1H),
5.89 (s, 1H), 7.18–7.69 (m, 10H), 7.85 (s, 1H) ppm.
13C NMR (100 MHz, CDCl3): δ 37.3, 62.2, 121.8,
128.3, 128.4, 128.8, 129.0, 129.0, 129.5, 130.5, 137.2
(JSe-C = 5.3 Hz), 139.7, 143.3, 161.1 ppm. IR (NaCl)
3055, 3027, 2921, 1649, 1624 (C N), 1592, 1574,
1495, 1448, 1338, 1189, 1092, 981, 885, 757, 694,
629, 556 cm–1; MS (EI) m/z (relative intensity, %)
315 (M+, 15), 234 (100), 224 (22), 210 (11), 195 (14),
157 (33); Anal. HRMS (EI) calcd for C17H17NSe:
315.0526, Found 315.0528.
Te-Phenyl
phenethyl(propa-1,2-dien-1-yl)carb-
amotelluroate 8c. The corresponding tellurium
analogue 8c was prepared in a similar proce-
dure as described for 8a. 1H NMR (400 MHz,
CDCl3): δ = 2.87 (t, J = 7.8 Hz, 2H), 2.99 (t,
J = 7.8 Hz, 2H), 3.49 (t, J = 7.8 Hz, 2H), 3.74
(t, J = 7.8 Hz, 2H), 5.38–5.40 (m, 2H), 5.51–
5.53 (m, 2H), 6.24–6.27 (m, 2H), 7.17–7.41
(m, 16H), 7.72–7.90 (m, 4H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 34.1, 35.0, 48.9, 50.4, 86.5,
87.6, 98.0, 100.2, 114.2, 114.9, 126.4, 126.9, 128.5,
128.8, 128.9, 129.0, 129.1, 129.4, 137.8, 138.4, 140.4,
140.5, 155.6, 156.3, 202.2, 203.4 ppm. IR (NaCl)
3055, 3026, 2938, 1656 (C O), 1435, 1376, 1246,
1141, 999, 733, 699 cm–1; MS (EI) m/z (relative
intensity, %) 393 (M+, 4), 365 (13), 234 (14), 207
(15), 186 (22), 144 (27), 105 (100); Anal. Calcd for
C18H17NOTe: C, 55.30; H, 4.38; N, 3.58, Found C,
55.02; H, 4.16; N, 3.54.
3-Methyl-1-phenethylazet-2(1H)-one
11. 1H
NMR (400 MHz, CDCl3): δ = 2.06 (s, 3H), 2.85 (t,
J = 8.0 Hz, 2H), 3.68 (dd, J = 2.7, 5.0 Hz, 2H), 6.06
(s, 1H), 7.15–7.65 (m, 5H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 19.2, 34.1, 51.0, 126.1, 126.4, 126.5,
127.1, 127.6, 128.6, 128.6, 128.7, 128.7, 128.7, 128.8,
128.9, 128.9, 129.0, 129.1, 129.2, 129.5, 135.2, 136.3,
136.3, 136.7, 138.3, 139.7, 165.0 ppm.
(E)-N-phenethyl-2-(phenyltellanyl)prop-2-en-1-
imine 10c. 1H NMR (400 MHz, CDCl3): δ 2.95 (t,
J = 7.3 Hz, 2H), 3.78 (t, J = 6.8 Hz, 2H), 5.46 (s,
1H), 6.38 (s, 1H), 7.18–7.41 (m, 8H), 7.73 (s, 1H),
7.88–7.90 (m, 2H) ppm. Nuclear Overhauser effect
experiment; irradiation at δ 7.73 (Ha) resulted in
7.6% enhancement of signal at δ 3.78 (Hb) and 6.2%
Se-Phenyl
N-benzyl-N-propa-1,2-dien-1-ylcarb-
amoselenoate 8b. The corresponding analogue 8b
was prepared in a similar procedure as described
for 8a. 1H NMR (400 MHz, CDCl3): δ = 4.73 (s, 2H),
Heteroatom Chemistry DOI 10.1002/hc

524 Shiro et al.
enhancement of signal at δ 6.38 (Hc); 13C NMR (100
MHz, CDCl3) δ 37.2, 61.4, 112.9, 126.1, 127.9, 128.3,
128.6, 129.1, 129.5, 133.4, 139.8, 141.7, 162.9 ppm.
IR (NaCl) 3026, 2925, 2840, 1629 (C N), 1585, 1433,
901, 735, 696 cm–1; MS (EI) m/z (relative intensity,
%) 365 (M+, 31), 274 (15), 234 (44), 207 (44),
144 (100); Anal. HRMS (EI) calcd for C17H17NTe:
365.0423, Found 365.0419.
raux, G.; Lam, H. W. J Am Chem Soc 2010, 132,
14373.
[8] Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria,
G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.;
Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji,
H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov,
A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada,
M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;
Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai,
H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.;
Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.;
Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi,
R.; Normand, J.; Raghavachari, K.; Rendell, A.;
Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.;
Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross,
J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts,
R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi,
R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.;
Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Sal-
vador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels,
A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.;
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Gaussian: Wallingford, CT, 2009.
ACKNOWLEDGEMENTS
Daisuke Shiro expresses his special thanks to the
JSPS Japanese–German Graduate Externship Pro-
gram on “Environmentally Benign Bio- and Chem-
ical Processes” for financial support of the stay in
RWTH, Aachen, Germany.
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Heteroatom Chemistry DOI 10.1002/hc