Nickel-catalyzed regio- and stereoselective hydrophosphinylation of internal ynamides with H-phosphinates

Article abstract of DOI:10.1016/j.tet.2018.10.042

A method for the catalytic hydrophosphinylation of internal ynamides with H-phosphinates has been developed for the first time. The protocol employing the catalyst generated from NiBr₂ and PPh₃ could be applied to several types of ynamides and H-phosphinates, affording (E)-β-aminovinylphosphinates in a highly regio- and stereoselective manner.

Full text of DOI:10.1016/j.tet.2018.10.042

Tetrahedron xxx (2018) 1e6
Contents lists available at ScienceDirect
Tetrahedron
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Nickel-catalyzed regio- and stereoselective hydrophosphinylation of
internal ynamides with H-phosphinates
,
*
Atsushi Kinbara a, Haruka Kasai a, Kaede Sato a, Yuri Watanabe a, Takehiro Yamagishi b
a School of Pharmacy, Ohu University, 31-1 Misumido, Tomita-machi, Koriyama, Fukushima 963-8611, Japan
b Department of Medicinal Chemistry, Hokkaido University of Science, 15-4-1, Maeda 7-jo, Teine-ku, Sapporo, Hokkaido 006-8585, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
A method for the catalytic hydrophosphinylation of internal ynamides with H-phosphinates has been
developed for the first time. The protocol employing the catalyst generated from NiBr2 and PPh3 could be
applied to several types of ynamides and H-phosphinates, affording (E)-b-aminovinylphosphinates in a
Received 7 August 2018
Received in revised form
15 October 2018
Accepted 17 October 2018
Available online xxx
highly regio- and stereoselective manner.
© 2018 Elsevier Ltd. All rights reserved.
Keywords:
Hydrophosphinylation
Internal ynamides
Phosphinic acid derivatives
1. Introduction
proceeded efficiently in the presence of Cu(OAc)2 catalyst, giving
(E)-b-aminovinylphosphinates in high regio- and stereo-
Phosphinic acid derivatives are an important class of com-
pounds because of their usefulness in medicinal chemistry [1] and
selectivities. However, the method was limited to terminal yna-
mides because the reaction of internal ynamides resulted in
complicated mixtures. Therefore, alternative protocols of hydro-
phosphinylation to improve the substrate limitation are desirable.
A related report by Rabasso and co-workers revealed that hydro-
phosphonylation of internal ynamides with dialkyl phosphites
proceeded by using NiBr2 as a catalyst [16], while Kang and co-
workers disclosed a hydrophosphorylation of internal ynamides
with diaryl phosphine oxides under metal-free conditions [17]. In
this paper, we report a hydrophosphinylation of internal ynamides
organocatalysis [2]. Some
b-aminophosphinic acid derivatives
function as potent inhibitors for protease enzymes [3e5] and
integrin antagonists [6]. Several synthetic methods for these com-
pounds have been developed, involving nucleophilic addition of
(1,1-diethoxyethyl)methylphosphinate to imines [7], the Michael
addition of amines to vinylphosphinates [8], addition of hypo-
phosphorus acid to N-vinylphthalimide [9], and ring opening of N-
tosyl aziridines with phosphinic nucleophiles [10,11]. The transition
metal-catalyzed addition of H-phosphinates to alkenes and alkynes
is a powerful and efficient method for preparing phosphinic acid
derivatives [12,13]. Various alkynes are applicable to this hydro-
phosphinylation for the preparation of alkenylphosphinates;
however, examples of similar reactions employing ynamides [14],
which are amino alkynes containing an electron-withdrawing
substituent at the nitrogen atom and are useful synthons for
organic synthesis, had not been reported. In 2017, we succeeded in
the first development of Cu-catalyzed hydrophosphinylation of
catalyzed by NiBr2-PPh3, affording (E)-b-aminovinylphosphinates
in a highly regio- and stereoselective manner (Scheme 1).
2. Results and discussion
The requisite ynamides 2b and 2d were prepared by alkynyla-
tion of carbamates 1b and 1d according to Danheiser's method [18]
and Hsung's method [19], respectively (Scheme 2). Other com-
pounds 2a [15], 2c [20], 2e, g, h, j [21], 2f [22], 2i [23], and 2k [24]
were prepared according to literature procedures.
In order to achieve the desired transformation, internal ynamide
2a and H-phosphinate 3a were employed as model substrates to
optimize the reaction parameters, in particular the transition metal
catalysts (Table 1). When 2a was treated with 3a in the presence of
NiBr2 (10 mol %) in toluene at reflux for 2 h, the adduct 4 was
ynamides, followed by conversion of the products to
b-amino-
phosphinates (Scheme 1) [15]. The reactions of terminal ynamides
* Corresponding author.
E-mail address: yamagishi-t@hus.ac.jp (T. Yamagishi).
https://doi.org/10.1016/j.tet.2018.10.042
0040-4020/© 2018 Elsevier Ltd. All rights reserved.
Please cite this article in press as: A. Kinbara, et al., Nickel-catalyzed regio- and stereoselective hydrophosphinylation of internal ynamides with
H-phosphinates, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.10.042

2
A. Kinbara et al. / Tetrahedron xxx (2018) 1e6
Fig. 1. NOE correlation of 4.
(entry 2). The use of NiI2 and Ni(acac)2 decreased the chemical
yields in comparison with that of NiBr2 (entries 3 and 4). Other
metal complexes with affinities for p-electrons such as PdCl2, FeCl2,
AgCl, and AuCl failed to catalyze the reaction (entries 5e8). It is
clear that the reactivity depended upon the ligands, since
employing PPh3 (20 mol %) in combination with NiBr2 led to an
increase in the chemical yield (76%, entry 9). The yield was signif-
icantly improved up to 99% by loading 40 mol % of PPh3 (entry 10).
When the reaction was carried out using less bulky PPh2Me in place
of PPh3, which has been shown to be effective ligand for the related
Ni-catalyzed hydrophosphonylation of alkynes [25], the yield was
decreased to 37% (entry 11). The use of P(o-Tol)3 and more basic
P(n-Bu)3 resulted in similar decreased chemical yields (entries 12
and 13). The reactions using bidentate ligands (dppe, dppp, bipy,
phen) were examined, however, no product or only a trace amount
of 4 was observed. The results demonstrate PPh3 is a good ligand for
the present hydrophosphinylation among those examined. The
reaction at room temperature proceeded quite sluggishly,
providing 4 in a low yield after 24 h (entry 14), thus indicating that
toluene at reflux was necessary for the reaction to proceed.
Ni(cod)2 and PPh3 were also found to catalyze the reaction effi-
ciently, which suggested that zerovalent nickel species might be
associated with the catalysis (entry 15).
Scheme 1. Catalytic hydrophosphinylation of terminal and internal ynamides.
Scheme 2. Preparation of ynamides.
Table 1
Optimization of reaction conditions.
Entry
Catalyst
Ligand (mol %)
Time (h)
Yield (%)a
1
2
3
4
5
6
7
NiBr2
NiCl2
NiI2
Ni(acac)2
PdCl2
FeCl2
AgCl
None
None
None
None
None
None
None
2
2
2
6
2
18
2
55
0
46
15
0
With the reaction conditions optimized, the scope of ynamide
substrates 2b-k was examined (Table 2). The hydrophosphinylation
of 2b, which contained an ethoxycarbonyl group in place of Cbz,
with 3a proceeded regio- and stereoselectively to give 5 in 99%
yield (entry 1). The E stereochemistry of 5 was verified by NOE.
Ynamides 2c having a tosyl group and 2d having a phenyl group on
the nitrogen atom also furnished the target products 6 and 7 in 78%
and 97% yields, respectively (entries 2 and 3). Aryl-substituted
ynamides 2e-h proved to be applicable substrates (entries 4e7),
although the reaction of 2h bearing a 4-chlorophenyl group only
gave a moderate chemical yield, which might be ascribed to
insertion of the catalyst into the aromatic CeCl bond [26]. On the
other hand, the reactions of ethoxycarbonyl- and TIPS-substituted
ynamides 2i and 2j did not afford the desired products resulting
in complicated mixtures, wherein each ynamide was not recovered
(Table 2, entries 8 and 9). When the terminal ynamide 2k was
employed, only a trace amount of the product was formed (entry
10). Our previous work demonstrated that Cu(OAc)2-catalyzed
hydrophosphinylation of 2k with 3a gave the product in good yield
(90%) [15], therefore, the catalytic system utilizing NiBr2-PPh3 for
internal ynamides was complementary to our previous method-
ology for terminal ynamides.
Trace
0
8
9
AuCl
None
2
2
2
2
2
2
24
3
0
NiBr2
NiBr2
NiBr2
NiBr2
NiBr2
NiBr2
Ni(cod)2
PPh3 (20)
PPh3 (40)
PPh2Me (40)
P(o-Tol)3 (40)
P(n-Bu)3 (40)
PPh3 (40)
PPh3 (40)
76
99
37
50
41
19
80
10
11
12
13
14b
15
a
Isolated yield.
Carried out at room temperature.
b
obtained in 55% yield (entry 1). The formation of other isomers
could not be detected by 1H and 31P NMR analysis of the crude
products, indicating the reaction proceeded in a highly regio- and
stereoselective manner. The stereochemistry of 4 was confirmed to
be the E configuration by NOE experiments (Fig. 1). The reagent
NiCl2 could not catalyze the reaction, with 61% of 2a recovered
Please cite this article in press as: A. Kinbara, et al., Nickel-catalyzed regio- and stereoselective hydrophosphinylation of internal ynamides with
H-phosphinates, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.10.042

A. Kinbara et al. / Tetrahedron xxx (2018) 1e6
3
Table 2
Substrate scope for ynamides.
Entry
2
Product
Time (h)
Yield (%)a
1
2
3
2b
2c
2d
PG ¼ CO2Et, R1 ¼ Bn
PG ¼ Ts, R1 ¼ Bn
5
6
7
2
4
2
99
78
97
PG ¼ CO2Et, R1 ¼ Ph
On the basis of these experimental results and related reports,
the catalytic cycle for the present hydrophosphinylation is pro-
posed as illustrated in Scheme 3. The zerovalent Ni(cod)2 as well as
NiBr2 was found to catalyze the reaction efficiently (Table 1), thus,
we consider Ni(Ⅱ)/Ni(0) catalytic cycle would proceed. Montchamp
and co-workers elucidated that reduction of NiCl2 with an alkyl
phosphinate occurred to form a Ni(0) species [13a], therefore, we
also propose that a Ni(0) species might be generated from NiBr2
and ligand (Ln) through reduction with H-phosphinate 3a. The
subsequent reaction of this nickel species with 3a would afford
complex A via oxidative addition [12a,13d] or complexation of Ni(0)
4
5
6
7
2e
2f
2g
2h
X ¼ H
8
9
10
11
4
4
6
6
97
77
83
55
X ¼ CO2Me
X ¼ MeO
X ¼ Cl
to the P(III) phosphinate tautomer [13a]. A then undergoes
p-
complexation with ynamide 2a to provide B. Next, HeNi addition to
the CeC triple bond occurs to form syn adduct C, and subsequent
reductive elimination affords the product 4 with regeneration of
the Ni(0) species. Insertion of CeC triple bond into the HeNi bond,
rather than into the P(O)eNi, would take place, because theoretical
study on Ni-catalyzed hydrophosphorylation of alkynes by Anani-
kov and co-workers reported alkyne insertion into the M-H bond
should be much easier compared to alkyne insertion into the M-P
bond [27]. Although exact reason for high regioselectivity remained
unclear, it might be associated with interaction between partially
8
9
10
2i
2j
2k
R ¼ CO2Et
R ¼ TIPS
R ¼ H
12
13
14
6
2
2
0
0
trace
a
Isolated yield.
negative charged hydrogen of HeNi and partially positive charged
a
carbon of ynamides because of their polarization of triple bond by
nitrogen atom in the complex B [14]. We proposed that the role of
ligand PPh3 would be to stabilize the unstable Ni(0) species, and
contribute to promoting reductive elimination from the complex C.
A theoretical study on Ni- and Pd-catalyzed Heck reactions sug-
gested that conversion of Ni(Ⅱ) into Ni(0) by reductive elimination
of hydrogen halide after b-hydride elimination would be relatively
difficult to proceed due to the unstable Ni(0) species [28]. However,
the detailed role of PPh3, such as steric and electronic effect, is not
clear at present. The proposed catalytic cycle is different from that
of the related hydrophosphonylation [16], wherein Ni(Ⅱ) is an
active catalyst simply acting as a strong Lewis acid to activate
electron-rich triple bond of ynamides.
The substrate scope for H-phosphinates 3b-f was subsequently
investigated (Table 3). The reaction of 2a with 3b having an iso-
propyl phosphinate moiety instead of ethyl phosphinate 3a gave
the product 15 in 90% yield (entry 1). The use of tert-butyl phos-
phinate 3c brought about a deterioration in chemical yield, prob-
ably due to steric hindrance (entry 2). Compounds 3d possessing a
decyl phosphinate moiety and 3e with a benzyl group on the
phosphorus atom worked well under the present conditions (en-
tries 3 and 4). However, the reaction with 3f containing a 1,1-
diethoxyethyl group resulted in a complicated mixture, which
might be due to decomposition of the acetal moiety by Lewis acidic
NiBr2 (entry 5).
Table 3
Substrate scope for H-phosphinates.
Entry
3
Product
Time (h)
Yield (%)a
1
2
3
4
5
3b
3c
3d
3e
3f
R2 ¼ Ph, R3 ¼ i-Pr
R2 ¼ Ph, R3 ¼ t-Bu
R2 ¼ Ph, R3 ¼ Dec
R2 ¼ Bn, R3 ¼ Et
15
16
17
18
19
2
5
3
4
2
90
48
86
75
0
R2 ¼ C(OEt)2Me, R3 ¼ Et
a
Isolated yield.
Scheme 3. Possible reaction mechanism.
Please cite this article in press as: A. Kinbara, et al., Nickel-catalyzed regio- and stereoselective hydrophosphinylation of internal ynamides with
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4
A. Kinbara et al. / Tetrahedron xxx (2018) 1e6
3. Conclusion
1.43e1.26 (9H, m), 0.88 (3H, t, J ¼ 6.9 Hz); 13C NMR (125 MHz,
CDCl3) d: 154.8, 140.0, 128.7 (2C), 126.4, 124.4 (2C), 73.8, 69.7, 63.3,
In conclusion,
a
highly regio- and stereoselective hydro-
31.3, 28.8, 28.5, 22.5, 18.4, 14.3, 14.0; HRMS (FABþ) calcd for
phosphinylation of internal ynamides catalyzed by NiBr2-PPh3 was
achieved. The present method was applicable to alkyl- and aryl-
substituted internal ynamides containing N-Ts and N-Cbz groups,
and H-phosphinates with less bulky alkyl groups. Both internal and
C
17H24NO2 ([MþH]þ) 274.1807, found 274.1827.
4.3. Typical procedure for the catalytic hydrophosphinylation of
internal ynamides
terminal ynamides could be applied to the synthesis of b-amino-
phosphinic acid derivatives by using this and our previously
developed method. Investigations into a detailed reaction mecha-
nism and the preparation of biologically active compounds are now
underway.
To a solution of H-phosphinate 3a (24.5 mg, 0.144 mmol) and
ynamide 2a (54.6 mg, 0.156 mmol) in toluene (2.0 mL) was added
NiBr2 (3.0 mg, 13.6 mmol) and PPh3 (14.3 mg, 54.4 mmol) at room
temperature under an Ar atmosphere and the mixture was refluxed
for 2 h. After the mixture was cooled to room temperature, it was
added H2O and was extracted AcOEt. The organic layer was washed
with H2O and brine, and dried over MgSO4, filtered and concen-
trated under reduced pressure. The residue was purified by a pre-
parative TLC (AcOEt) to give alkenylphosphinate 4 (74.0 mg, 99%
yield) as a colorless oil.
4. Experimental
All melting points were obtained on a Yanagimoto micromelting
point apparatus and are uncorrected. IR spectra were recorded on a
JASCO FTIR-4100 instrument. Mass spectra were measured on a
JEOL JMS-MS700V instrument by FABþ. NMR spectra were obtained
on a JEOL JNM-ECA500 instrument. The chemical shift data for each
4.4. Benzyl (E)-benzyl(2-(ethoxy(phenyl)phosphoryl)oct-1-en-1-yl)
carbamate 4
signal on 1H NMR are given in units of
d
relative to CHCl3 (
for CDCl3 solution. For 13C NMR spectra, the chemical shifts in CDCl3
are recorded relative to the CDCl3 resonance (
¼ 77.0). The chem-
d
¼ 7.26)
d
Colorless oil; IR (neat) cmꢁ1: 2956, 2928, 1715, 1622, 1496, 1455,
ical shifts of 31P are recorded relative to external 85% H3PO4 (
d
¼ 0)
1438; 31P NMR (202 MHz, CDCl3) : 35.3; 1H NMR (500 MHz, CDCl3)
d
with broad-band 1H decoupling. Commercial reagents were used as
received. Starting materials 3a [29], 3b [30], 3c [31], 3d [32], 3e [33],
and 3f [34] were prepared according to literature procedures.
d
: 7.65 (2H, dd, J ¼ 11.5, 8.0 Hz), 7.48 (1H, t, J ¼ 7.5 Hz), 7.39e7.24
(11H, m), 7.17 (2H, d, J ¼ 6.9 Hz), 5.20 (2H, s), 4.79 (2H, q,
J ¼ 16.0 Hz), 3.98e3.90 (2H, m), 2.04e1.95 (2H, m), 1.25 (3H, t,
J ¼ 6.9 Hz), 1.21e0.97 (8H, m), 0.79 (3H, t, J ¼ 7.5 Hz); 13C NMR
4.1. Ethyl benzyl(oct-1-yn-1-yl)carbamate 2b
(125 MHz, CDCl3)
d: 154.7, 138.4 (d, JPC ¼ 22.8 Hz), 137.0, 135.6, 131.8
(d, JPC ¼ 2.4 Hz), 131.7, 131.5 (2C, d, JPC ¼ 9.6 Hz), 128.6 (2C), 128.5
(2C), 128.4, 128.3, 128.3, 128.2, 128.1 (2C), 127.4 (2C), 126.9, 68.4,
60.7 (d, JPC ¼ 4.8 Hz), 50.9, 31.2, 29.3, 28.7, 27.0 (d, JPC ¼ 8.4 Hz), 22.4,
16.3 (d, JPC ¼ 7.2 Hz), 14.0; HRMS (FABþ) calcd for C31H39NO4P
([MþH]þ) 520.2617, found 520.2665.
To a solution of 1b (1.57 g, 6.67 mmol) in pyridine (39.0 mL) was
added THF (6.0 mL) and KHMDS (0.5 M toluene solution, 13.5 mL,
6.74 mmol) at 0 ꢀC under an Ar atmosphere, and the mixture was
stirred at the same temperature for 10 min. To the mixture was
added CuI (1.27 g, 6.67 mmol) at 0 ꢀC, and the mixture was stirred at
room temperature for 2 h. Then, to the mixture was added a solu-
tion of 1-iodooct-1-yne (2.36 g, 10.0 mmol) in THF (7.0 mL) at room
temperature, and the mixture was stirred at same temperature for
15 h. The reaction mixture was diluted with brine and extracted
with Et2O. The organic layer was washed with brine, dried over
MgSO4, filtered and concentrated under reduced pressure. The
residue was purified by a silica gel column chromatography (hex-
ane/AcOEt ¼ 20: 1) to give 2b (710 mg, 37% yield) as a colorless oil:
IR (neat) cmꢁ1: 2929, 2262, 1718, 1496, 1455; 1H NMR (500 MHz,
4.5. Ethyl (E)-benzyl(2-(ethoxy(phenyl)phosphoryl)oct-1-en-1-yl)
carbamate 5
This compound (61.7 mg, 99%) was prepared from 3a (23.2 mg,
0.136 mmol) with 2b (43.1 mg, 0.150 mmol). Colorless oil; IR (neat)
cmꢁ1: 2956, 2928, 2855, 1715, 1620, 1496, 1437; 31P NMR (202 MHz,
CDCl3)
d
: 35.6; 1H NMR (500 MHz, CDCl3)
d
: 7.68 (2H, dd, J ¼ 12.0,
7.5 Hz), 7.42 (1H, m), 7.42e7.23 (6H, m), 7.18 (2H, d, J ¼ 6.9 Hz), 4.80
(2H, dd, J ¼ 34.4, 16.0 Hz), 4.24 (2H, q, J ¼ 6.9 Hz), 4.02e3.93 (2H,
m), 2.04e1.96 (2H, m), 1.31e1.00 (14H, m), 0.85 (3H, t, J ¼ 6.9 Hz);
CDCl3)
d
: 7.35e7.29 (5H, m), 4.59 (2H, s), 4.23 (2H, q, J ¼ 6.9 Hz),
2.24 (2H, t, J ¼ 6.9 Hz),1.44 (2H, t, J ¼ 7.5 Hz),1.35e1.22 (9H, m), 0.88
13C NMR (125 MHz, CDCl3)
d: 154.9, 138.6 (d, JPC ¼ 22.8 Hz), 137.2,
(3H, t, J ¼ 6.9 Hz); 13C NMR (125 MHz, CDCl3)
d: 155.7, 136.4, 128.4
132.0, 131.8, 131.8, 131.5, 131.5, 130.9, 128.6 (2C), 128.3, 128.2, 127.3,
126.7, 62.8, 60.5 (d, JPC ¼ 6.0 Hz), 50.4, 31.2, 29.3, 28.8 (d,
JPC ¼ 2.4 Hz), 26.9 (d, JPC ¼ 9.6 Hz), 22.4, 16.4 (d, JPC ¼ 7.2 Hz), 14.4,
13.9; HRMS (FABþ) calcd for C26H37NO4P ([MþH]þ) 458.2460, found
458.2517.
(2C), 128.3, 127.7 (2C), 63.0, 53.6, 31.3, 28.9, 28.3, 22.5, 18.4, 14.4,
14,0, (two signal was missing); HRMS (FABþ) calcd for C18H26NO2
([MþH]þ) 288.1964, found 288.1983.
4.2. Ethyl oct-1-yn-1-yl(phenyl)carbamate 2d
4.6. Ethyl (E)-(1-(N-benzyl-4-methylphenylsulfonamido)oct-1-en-
A
mixture of 1-bromooct-1-yne (330 mg, 2.00 mmol), 1d
2-yl)(phenyl)phosphinate 6
(416 mg, 2.20 mmol), K3PO4 (849 mg, 4.00 mmol), CuSO4‧5H2O
(50.0 mg, 0.200 mmol) and 1,10-phenanthroline‧H2O (72.0 mg,
0.400 mmol) in toluene (10.0 mL) was stirred at the 80 ꢀC for 48 h.
After the mixture was cooled to room temperature, it filtered
through a short path silica gel column. The filtrate was concen-
trated under reduced pressure to give the residue, which was pu-
rified by a silica gel column chromatography (hexane/AcOEt ¼ 30:
This compound (57.3 mg, 78%) was prepared from 3a (23.3 mg,
0.136 mmol) with 2c (63.0 mg, 0.170 mmol). Colorless oil; IR (neat)
cmꢁ1: 2925, 2854, 1618, 1496, 1455, 1439; 31P NMR (202 MHz,
CDCl3)
d
: 33.6; 1H NMR (500 MHz, CDCl3)
d
: 7.65 (2H, d, J ¼ 8.6 Hz),
7.58e7.48 (3H, m), 7.40 (2H, dt, J ¼ 7.5, 3.4 Hz), 7.32 (2H, d,
J ¼ 8.0 Hz), 7.25e7.20 (5H, m), 6.64 (1H, d, J ¼ 14.9 Hz), 4.41 (2H, s),
3.99e3.83 (2H, m), 2.45 (3H, s), 2.12e1.95 (2H, m), 1.29e1.25 (4H,
m), 1.10 (2H, quin, J ¼ 6.9 Hz), 1.00e0.91 (5H, m), 0.80 (3H, t,
1) to give 2d (435 mg, 80% yield) as a pale yellow oil: IR (neat) cmꢁ1
:
:
2929, 2268, 1732, 1596, 1492, 1458; 1H NMR (500 MHz, CDCl3)
d
7.48 (2H, d, J ¼ 7.5 Hz), 7.35 (2H, t, J ¼ 7.5 Hz), 7.24 (1H, t, J ¼ 7.5 Hz),
J ¼ 7.5 Hz); 13C NMR (125 MHz, CDCl3)
d: 144.2, 137.4 (d,
4.29 (2H, q, J ¼ 6.9 Hz), 2.33 (2H, t, J ¼ 6.9 Hz), 1.55e1.51 (2H, m),
JPC ¼ 21.6 Hz), 135.4, 134.9, 132.0, 132.0, 131.6 (d, JPC ¼ 122.4 Hz),
Please cite this article in press as: A. Kinbara, et al., Nickel-catalyzed regio- and stereoselective hydrophosphinylation of internal ynamides with
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A. Kinbara et al. / Tetrahedron xxx (2018) 1e6
5
131.4, 131.3, 129.9 (2C), 128.5 (2C), 128.4, 128.3, 128.2 (2C), 127.8,
127.4 (2C), 60.5 (d, JPC ¼ 6.0 Hz), 53.4, 31.3, 29.4, 28.3, 27.5 (d,
JPC ¼ 8.4 Hz), 22.4, 21.6, 16.3 (d, JPC ¼ 7.2 Hz), 14.0; HRMS (FABþ)
calcd for C30H39NO4PS ([MþH]þ) 540.2337, found 540.2388.
0.129 mmol) with 2g (58.7 mg, 0.150 mmol). Colorless oil; IR (neat)
cmꢁ1: 2980, 1600, 1508, 1454, 1439; 31P NMR (202 MHz, CDCl3)
31.6; 1H NMR (500 MHz, CDCl3)
d
:
d
: 7.78 (1H, d, J ¼ 16.0 Hz), 7.68 (2H,
d, J ¼ 8.6 Hz), 7.43e7.39 (3H, m), 7.31e7.27 (4H, m), 7.14e7.09 (3H,
m), 6.70 (2H, d, J ¼ 6.9 Hz), 6.50 (2H, d, J ¼ 8.6 Hz), 6.41 (2H, d,
J ¼ 7.5 Hz), 4.31 (2H, dd, J ¼ 67.0, 16.6 Hz), 3.95e3.88 (2H, m), 3.71
(3H, s), 2.45 (3H, s), 1.23 (3H, t, J ¼ 6.9 Hz); 13C NMR (125 MHz,
4.7. Ethyl (E)-(2-(ethoxy(phenyl)phosphoryl)oct-1-en-1-
yl)(phenyl)carbamate 7
CDCl3)
d: 156.1 (d, JPC ¼ 2.4 Hz), 144.3, 136.8 (d, JPC ¼ 22.8 Hz), 135.9,
This compound (58.8 mg, 97%) was prepared from 3a (23.2 mg,
0.136 mmol) with 2d (41.5 mg, 0.150 mmol). Colorless oil; IR (neat)
cmꢁ1: 2962, 2927, 2857, 1723, 1620, 1593, 1496, 1463, 1439; 31P
135.4, 131.7, 131.7 (2C, d, JPC ¼ 9.6 Hz), 131.5 (2C, d, JPC ¼ 4.8 Hz),
130.8 (d, JPC ¼ 139.2 Hz), 129.9 (2C), 128.7 (d, JPC ¼ 13.2 Hz), 128.0,
128.0 (2C), 127.9, 127.2 (2C), 127.0, 126.7 (2C), 124.3 (d, JPC ¼ 7.2 Hz),
116.3 (d, JPC ¼ 133.2 Hz), 113.2, 60.7 (d, JPC ¼ 6.0 Hz), 55.1, 49.9, 21.6,
16.3 (d, JPC ¼ 6.0 Hz); HRMS (FABþ) calcd for C31H33NO5PS
([MþH]þ) 562.1817, found 562.1773.
NMR (202 MHz, CDCl3) d d: 7.79
: 35.8; 1H NMR (500 MHz, CDCl3)
(2H, dd, J ¼ 12.0, 6.9 Hz), 7.68 (1H, d, J ¼ 17.2 Hz), 7.52 (1H, t,
J ¼ 6.9 Hz), 7.47e7.44 (2H, m), 7.35 (2H, t, J ¼ 7.5 Hz), 7.29 (1H, t,
J ¼ 6.9 Hz), 7.22 (2H, d, J ¼ 7.5 Hz), 4.23 (2H, q, J ¼ 6.9 Hz), 4.12e4.02
(2H, m), 1.47e1.39 (2H, m), 1.36 (3H, t, J ¼ 6.9 Hz), 1.25 (3H, t,
J ¼ 6.9 Hz), 1.06 (2H, quin, J ¼ 7.5 Hz), 0.95e0.80 (4H, m), 0.76 (3H, t,
4.11. Ethyl (E)-(2-(N-benzyl-4-methylphenylsulfonamido)-1-(4-
chlorophenyl)vinyl)(phenyl)phosphinate 11
J ¼ 7.5 Hz), 0.67 (2H, quin, J ¼ 7.5 Hz); 13C NMR (125 MHz, CDCl3)
d:
154.3, 139.6, 138.5 (d, JPC ¼ 24.0 Hz), 131.8, 131.8, 131.7, 131.7, 131.5
(d, JPC ¼ 135.6 Hz), 128.9 (2C), 128.4, 128.3, 127.6 (2C), 127.4, 63.0,
60.6 (d, JPC ¼ 6.0 Hz), 31.2, 29.1, 28.6, 25.8 (d, JPC ¼ 7.2 Hz), 22.3, 16.4
(d, JPC ¼ 7.2 Hz), 14.3, 13.9; HRMS (FABþ) calcd for C25H35NO4P
([MþH]þ) 444.2304, found 444.2356.
This compound (42.0 mg, 55%) was prepared from 3a (23.2 mg,
0.136 mmol) with 2h (59.4 mg, 0.150 mmol). Colorless oil; IR (neat)
cmꢁ1: 2979, 1602, 1488, 1439; 31P NMR (202 MHz, CDCl3) : 31.1; 1H
d
NMR (500 MHz, CDCl3)
d
: 7.84 (1H, d, J ¼ 16.6 Hz), 7.69 (2H, d,
J ¼ 8.0 Hz), 7.46e7.39 (3H, m), 7.33e7.30 (4H, m), 7.15e7.09 (3H, m),
6.89 (2H, d, J ¼ 8.6 Hz), 6.65 (2H, d, J ¼ 7.5 Hz), 6.39 (2H, d,
J ¼ 6.9 Hz), 4.30 (2H, dd, J ¼ 69.3, 16.6 Hz), 3.94 (2H, dt, J ¼ 7.5,
2.3 Hz), 2.46 (3H, s), 1.25 (3H, t, J ¼ 6.9 Hz); 13C NMR (125 MHz,
4.8. Ethyl (E)-(2-(N-benzyl-4-methylphenylsulfonamido)-1-
phenylvinyl)(phenyl)phosphinate 8
CDCl3)
d
: 144.6, 137.1 (d, JPC ¼ 21.6 Hz), 135.6, 135.0, 133.8 (d,
This compound (70.0 mg, 97%) was prepared from 3a (23.2 mg,
0.136 mmol) with 2e (61.5 mg, 0.170 mmol). Colorless oil; IR (neat)
JPC ¼ 3.6 Hz), 133.0, 131.9 (d, JPC ¼ 2.4 Hz), 131.8, 131.7, 131.7, 130.9,
130.8, 130.4 (d, JPC ¼ 140.4 Hz), 130.0 (2C), 128.6 (d, JPC ¼ 13.2 Hz),
128.2, 128.1 (2C), 127.7, 127.3 (2C), 127.1, 126.3 (2C), 114.9 (d,
JPC ¼ 134.4 Hz), 60.9 (d, JPC ¼ 6.0 Hz), 50.1, 21.6, 16.3 (d, JPC ¼ 7.2 Hz);
HRMS (FABþ) calcd for C30H30ClNO4PS ([MþH]þ) 566.1322, found
566.1272.
cmꢁ1: 1615, 1594, 1492, 1469; 31P NMR (202 MHz, CDCl3) : 31.3; 1H
d
NMR (500 MHz, CDCl3)
d
: 7.84 (1H, d, J ¼ 16.0 Hz), 7.68 (2H, d,
J ¼ 8.0 Hz), 7.43e7.38 (3H, m), 7.32e7.27 (4H, m), 7.15e7.08 (4H, m),
6.96 (2H, t, J ¼ 8.0 Hz), 6.65 (2H, d, J ¼ 7.5 Hz), 6.47 (2H, d,
J ¼ 8.0 Hz), 4.28 (2H, dd, J ¼ 76.8, 16.6 Hz), 3.98e3.87 (2H, m), 2.45
(3H, s), 1.23 (3H, t, J ¼ 7.5 Hz); 13C NMR (125 MHz, CDCl3)
d: 144.4,
4.12. Benzyl (E)-benzyl(2-(isopropoxy(phenyl)phosphoryl)oct-1-
en-1-yl)carbamate 15
136.7 (d, JPC ¼ 21.6 Hz), 135.8, 135.3, 132.5 (d, JPC ¼ 7.2 Hz), 131.7,
131.7, 131.6, 130.7 (d, JPC ¼ 140.4 Hz), 130.4, 130.3, 129.9 (2C), 128.0,
128.0 (2C), 127.9, 127.7, 127.6, 127.6, 127.2 (2C), 127.0, 126.5 (2C),
116.3 (d, JPC ¼ 132.0 Hz), 60.7 (d, JPC ¼ 4.8 Hz), 49.8, 21.6, 16.3 (d,
JPC ¼ 7.2 Hz); HRMS (FABþ) calcd for C30H31NO4PS ([MþH]þ)
532.1711, found 532.1779.
This compound (65.3 mg, 90%) was prepared from 3b (25.0 mg,
0.136 mmol) with 2a (52.4 mg, 0.150 mmol). Colorless oil; IR (neat)
cmꢁ1: 2956, 2927, 1715, 1622, 1496, 1454, 1438; 31P NMR (202 MHz,
CDCl3) d d: 7.67e7.63 (2H, m), 7.47
: 33.5; 1H NMR (500 MHz, CDCl3)
(1H, t, J ¼ 6.9 Hz), 7.38e7.24 (11H, m), 7.17 (2H, d, J ¼ 6.9 Hz), 5.20
(2H, d, J ¼ 4.0 Hz), 4.79 (2H, dd, J ¼ 60.2, 16.0 Hz), 4.52 (1H, m),
2.05e1.92 (2H, m), 1.27e0.94 (14H, m), 0.78 (3H, t, J ¼ 7.5 Hz); 13C
4.9. Methyl (E)-4-(2-(N-benzyl-4-methylphenylsulfonamido)-1-
(ethoxy(phenyl)phosphoryl)vinyl)benzoate 9
NMR (125 MHz, CDCl3)
d: 154.8, 138.0 (d, JPC ¼ 21.6 Hz), 137.1, 135.7,
This compound (62.1 mg, 77%) was prepared from 3a (23.2 mg,
0.136 mmol) with 2f (62.9 mg, 0.150 mmol). Colorless oil; IR (neat)
132.6, 131.7, 131.7, 131.6, 131.5, 128.6 (2C), 128.5 (2C), 128.3 (2C),
128.2, 128.1 (2C), 127.4 (2C), 126.9, 69.8 (d, JPC ¼ 6.0 Hz), 68.3, 50.9,
31.2, 29.3, 28.7, 27.1 (d, JPC ¼ 8.4 Hz), 24.2 (d, JPC ¼ 3.6 Hz), 24.1 (d,
JPC ¼ 4.8 Hz), 22.4, 14.0; HRMS (FABþ) calcd for C32H41NO4P
([MþH]þ) 534.2773, found 534.2810.
cmꢁ1: 2980, 1720, 1605, 1496, 1438; 31P NMR (202 MHz, CDCl3)
d:
30.9; 1H NMR (500 MHz, CDCl3)
d
: 7.89 (1H, d, J ¼ 16.0 Hz), 7.69 (2H,
d, J ¼ 8.6 Hz), 7.61 (2H, d, J ¼ 8.0 Hz), 7.45e7.27 (7H, m), 7.14 (1H, t,
J ¼ 7.5 Hz), 7.08 (2H, t, J ¼ 7.5 Hz), 6.60 (2H, d, J ¼ 7.5 Hz), 6.54 (2H,
dd, J ¼ 8.6, 1.7 Hz), 4.27 (2H, dd, J ¼ 83.1, 16.6 Hz), 3.98e3.90 (2H,
m), 3.88 (3H, s), 2.47 (3H, s), 1.24 (3H, t, J ¼ 6.9 Hz); 13C NMR
4.13. Benzyl (E)-benzyl(2-(tert-butoxy(phenyl)phosphoryl)oct-1-
en-1-yl)carbamate 16
(125 MHz, CDCl3)
d
: 166.6, 144.6, 137.8 (d, JPC ¼ 7.2 Hz), 137.2 (d,
JPC ¼ 20.4 Hz), 135.6, 134.8, 131.9 (d, JPC ¼ 2.4 Hz), 131.7, 131.6, 130.5
(2C, d, JPC ¼ 4.8 Hz), 130.4 (d, JPC ¼ 141.6 Hz), 130.1 (2C), 129.2 (d,
JPC ¼ 2.4 Hz), 128.6 (2C), 128.2, 128.1 (2C), 128.1, 127.2 (2C), 127.2,
126.3 (2C), 115.3 (d, JPC ¼ 130.8 Hz), 60.9 (d, JPC ¼ 6.0 Hz), 52.1, 50.1,
21.6, 16.3 (d, JPC ¼ 7.2 Hz); HRMS (FABþ) calcd for C32H33NO6PS
([MþH]þ) 590.1766, found 590.1741.
This compound (35.9 mg, 48%) was prepared from 3c (27.0 mg,
0.136 mmol) with 2a (52.5 mg, 0.150 mmol). Colorless oil; IR (neat)
cmꢁ1: 2956, 2929, 1715, 1624, 1496, 1455, 1438; 31P NMR (202 MHz,
CDCl3) d d: 7.64e7.60 (2H, m), 7.44
: 29.5; 1H NMR (500 MHz, CDCl3)
(1H, t, J ¼ 6.9 Hz), 7.33e7.21 (11H, m), 7.18 (2H, d, J ¼ 6.9 Hz), 5.19
(2H, d, J ¼ 1.7 Hz), 4.76 (2H, dd, J ¼ 44.7, 16.0 Hz), 2.04e1.91 (2H, m),
1.40 (9H, s), 1.19e0.93 (8H, m), 0.79 (3H, t, J ¼ 7.5 Hz); 13C NMR
4.10. Ethyl (E)-(2-(N-benzyl-4-methylphenylsulfonamido)-1-(4-
(125 MHz, CDCl3) d: 137.1, 135.7, 134.6, 133.5, 131.3, 131.3, 131.3,
methoxyphenyl)vinyl)(phenyl)phosphinate 10
131.2, 128.6 (2C), 128.5 (2C), 128.3, 128.1 (2C), 128.0 (2C), 127.4 (2C),
127.1, 83.2 (d, JPC ¼ 8.4 Hz), 68.2, 51.1, 31.3, 30.7, 30.7 (2C), 29.4, 28.5,
27.2 (d, JPC ¼ 8.4 Hz), 22.4, 14.0; HRMS (FABþ) calcd for C33H43NO4P
This compound (60.1 mg, 83%) was prepared from 3a (22.0 mg,
Please cite this article in press as: A. Kinbara, et al., Nickel-catalyzed regio- and stereoselective hydrophosphinylation of internal ynamides with
H-phosphinates, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.10.042

6
A. Kinbara et al. / Tetrahedron xxx (2018) 1e6
[3] D.V. Patel, K. Rielly-Gauvin, D.E. Ryono, C.A. Free, W.L. Rogers, S.A. Smith,
([MþH]þ) 548.2930, found 548.2823.
J.M. DeForrest, R.S. Oehl, E.W. Petrillo Jr., J. Med. Chem. 38 (1995) 4557.
[4] B. Stowasser, K.-H. Budt, L. Jian-Qi, A. Peyman, D. Ruppert, Tetrahedron Lett.
33 (1992) 6625.
4.14. Benzyl (E)-benzyl(2-((decyloxy)(phenyl)phosphoryl)oct-1-en-
[5] E. Weglarz-Tomczak, L. Berlicki, M. Pawelczak, B. Nocek, Eur. J. Med. Chem.
117 (2016) 187.
1-yl)carbamate 17
[6] M. Bollinger, F. Manzenrieder, R. Kolb, A. Bochen, S. Neubauer, L. Marinelli,
V. Limongelli, E. Novellino, G. Moessmer, R. Pell, W. Lindner, J. Fanous,
A. Hoffman, H. Kessler, J. Med. Chem. 55 (2012) 871.
This compound (73.9 mg, 86%) was prepared from 3d (38.9 mg,
0.136 mmol) with 2a (52.4 mg, 0.150 mmol). Colorless oil; IR (neat)
cmꢁ1: 2924, 2854, 1717, 1623, 1496, 1455, 1438; 31P NMR (202 MHz,
[7] D. Zhang, C. Yuan, Chem. Eur. J. 15 (2009) 4088.
€
[8] (a) G. Markl, B. Merkl, Tetrahedron Lett. 22 (1981) 4459;
CDCl3)
d
: 35.1; 1H NMR (500 MHz, CDCl3)
d
: 7.64 (2H, dd, J ¼ 11.5,
(b) H. Krawczyk, Phosphorus, sulfur silicon 118 (1996) 195;
(c) J. Mortier, A.-D. Fortineau, M. Vaultier, Phosphorus, sulfur silicon 149
(1999) 221.
8.0 Hz), 7.48 (1H, t, J ¼ 6.9 Hz), 7.38e7.27 (11H, m), 7.17 (2H, d,
J ¼ 6.9 Hz), 5.20 (2H, d, J ¼ 1.7 Hz), 4.79 (2H, dd, J ¼ 26.4, 16.0 Hz),
3.88e3.81 (2H, m), 2.05e1.94 (2H, m), 1.63e1.60 (2H, m), 1.29e0.96
(22H, m), 0.88 (3H, t, J ¼ 6.9 Hz), 0.79 (3H, t, J ¼ 7.5 Hz); 13C NMR
ꢁ
[9] C. Queffelec, P. Ribiere, J.-L. Montchamp, J. Org. Chem. 73 (2008) 8987.
[10] M.E. Duggan, D.S. Karanewsky, Tetrahedron Lett. 24 (1983) 2935.
[11] For reviews of synthesis of
b-aminophosphinates, see: (a) F. Palacios,
C. Alonso, J.M. de los Santos, Chem. Rev. 105 (2005) 899;
(b) F. Palacios, C. Alonso, J.M. de los Santos, Curr. Org. Chem. 8 (2004) 1481.
[12] For reviews, see: (a) Q. Xu, Y.-B. Zhou, C.-Q. Zhao, S.-F. Yin, L.-B. Han, Mini Rev.
Med. Chem. 13 (2013) 824;
(125 MHz, CDCl3)
d
: 154.7,138.4 (d, JPC ¼ 22.8 Hz), 137.0,135.7,131.8,
131.8, 131.6, 131.5, 130.7, 128.6 (2C), 128.5 (2C), 128.4, 128.3 (2C),
128.1 (2C), 127.4 (2C), 126.9, 68.3, 64.6 (d, JPC ¼ 6.0 Hz), 50.9, 31.9,
31.3, 30.5, 30.4, 29.5, 29.3 (d, JPC ¼ 4.8 Hz), 29.2, 28.7, 27.1, 27.0, 25.6,
22.7, 22.4, 14.1, 14.0; HRMS (FABþ) calcd for C39H55NO4P ([MþH]þ)
632.3869, found 632.3877.
(b) J.-L. Montchamp, J. Organomet. Chem. 690 (2005) 2388.
[13] For selected examples, see: (a) S. Ortial, H.C. Fisher, J.-L. Montchamp, J. Org.
Chem. 78 (2013) 6599;
ꢁ
(b) P. Ribiere, K. Bravo-Altamirano, M.I. Antczak, J.D. Hawkins, J.-
L. Montchamp, J. Org. Chem. 70 (2005) 4064;
ꢁ
(c) S. Deprele, J.-L. Montchamp, J. Am. Chem. Soc. 124 (2002) 9386;
4.15. Benzyl (E)-benzyl(2-(benzyl(ethoxy)phosphoryl)oct-1-en-1-
yl)carbamate 18
(d) L.-B. Han, C.-Q. Zhao, S. Onozawa, M. Goto, M. Tanaka, J. Am. Chem. Soc.
124 (2002) 3842;
(e) M. Niu, H. Fu, Y. Zhao, Chem. Commun. (2007) 272.
[14] For reviews of ynamides, see: (a) X.-N. Wang, H.-S. Yeom, L.-C. Fang, S. He, Z.-
X. Ma, B.L. Kedrowski, R.P. Hsung, Acc. Chem. Res. 47 (2014) 560;
(b) K.A. DeKorver, H. Li, A.G. Lohse, R. Hayashi, Z. Lu, Y. Zhang, R.P. Hsung,
Chem. Rev. 110 (2010) 5064;
This compound (54.3 mg, 75%) was prepared from 3e (25.0 mg,
0.136 mmol) with 2a (58.9 mg, 0.169 mmol). Colorless oil; IR (neat)
cmꢁ1: 2956, 2922, 2855, 1715, 1622, 1496, 1454; 31P NMR (202 MHz,
CDCl3) d d: 7.34e7.15 (13H, m),
: 43.8; 1H NMR (500 MHz, CDCl3)
(c) G. Evano, A. Coste, K. Jouvin, Angew. Chem. Int. Ed. 49 (2010) 2840;
(d) A.R. Katritzky, R. Jiang, S.K. Singh, Heterocycles 63 (2004) 1455;
(e) J.A. Mulder, K.C.M. Kurtz, R.P. Hsung, Synlett (2003) 1379;
(f) C.A. Zificsak, J.A. Mulder, R.P. Hsung, C. Rameshkumar, L.-L. Wei, Tetrahe-
dron 57 (2001) 7575.
7.07e7.04 (3H, m), 5.17 (2H, d, J ¼ 4.6 Hz), 4.70 (2H, d, J ¼ 2.9 Hz),
3.92 (1H, m), 3.72 (1H, m), 3.09 (2H, m), 1.99e1.92 (2H, m),
1.25e1.07 (11H, m), 0.85 (3H, t, J ¼ 6.9 Hz); 13C NMR (125 MHz,
[15] A. Kinbara, M. Sato, K. Yumita, T. Yamagishi, Tetrahedron 73 (2017) 1705.
[16] A. Fadel, F. Legrand, G. Evano, N. Rabasso, Adv. Synth. Catal. 353 (2011) 263.
[17] H. Huang, H. Zhu, J.Y. Kang, Org. Lett. 20 (2018) 2778.
[18] J.R. Dunetz, R.L. Danheiser, Org. Lett. 5 (2003) 4011.
[19] Y. Zhang, R.P. Hsung, M.R. Tracey, K.C.M. Kurtz, E.L. Vera, Org. Lett. 6 (2004)
1151.
[20] H. Liu, Y. Yang, S. Wang, J. Wu, X.-N. Wang, J. Chang, Org. Lett. 17 (2015) 4472.
[21] B. Yao, Z. Liang, T. Niu, Y. Zhang, J. Org. Chem. 74 (2009) 4630.
[22] H. Wakamatsu, M. Takeshita, Synlett (2010) 2322.
[23] S.J. Mansfield, C.D. Campbell, M.W. Jones, E.A. Anderson, Chem. Commun. 51
(2015) 3316.
CDCl3)
d
: 154.5, 139.0 (d, JPC ¼ 21.6 Hz), 137.0, 135.6, 131.7, 131.6,
129.9, 129.9, 128.6 (2C), 128.5 (2C), 128.4, 128.3, 128.3, 128.1 (2C),
127.4 (2C), 126.8, 126.6 (d, JPC ¼ 2.4 Hz), 68.3, 60.3 (d, JPC ¼ 6.0 Hz),
50.9, 36.8 (d, JPC ¼ 96.0 Hz), 31.4, 29.5, 28.7, 27.3 (d, JPC ¼ 8.4 Hz),
22.5, 16.3 (d, JPC ¼ 6.0 Hz), 14.0; HRMS (FABþ) calcd for C32H41NO4P
([MþH]þ) 534.2773, found 534.2810.
Acknowledgments
[24] Y.-P. Wang, R.L. Danheiser, Tetrahedron Lett. 52 (2011) 2111.
[25] L.-B. Han, C. Zhang, H. Yazawa, S. Shimada, J. Am. Chem. Soc. 126 (2004) 5080.
[26] J. Heinicke, N. Gupta, A. Surana, N. Peulecke, B. Witt, K. Steinhauser,
R.K. Bansal, P.G. Jones, Tetrahedron 57 (2001) 9963.
The authors wish to thank Ohu University and Hokkaido Uni-
versity of Science for financial support.
[27] V.P. Ananikov, I.P. Beletskaya, Chem. Asian J. 6 (2011) 1423.
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Please cite this article in press as: A. Kinbara, et al., Nickel-catalyzed regio- and stereoselective hydrophosphinylation of internal ynamides with
H-phosphinates, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.10.042