Gold(I)-Catalyzed Synthesis of Six-Membered P,O-Heterocycles via Hydration/Intramolecular Cyclization Cascade Reaction

Article abstract of DOI:10.1002/adsc.201900605

Herein, we report the synthesis of six-membered P,O-heterocycles from dialkynylphosphine oxides. By using gold(I) complexes, the chemoselectivity of the reaction was switched from literature-reported double hydration to a hydration/intramolecular cyclization cascade. Control experiments indicated that the first alkyne hydration product is an intermediate of the reaction. In addition, a density functional theory (DFT) calculation allowed to rationalize the observed chemoselectivity. (Figure presented.).

Full text of DOI:10.1002/adsc.201900605

Title: Gold(I)-Catalyzed Synthesis of Six-Membered P,O-Heterocycles
via Hydration/Intramolecular Cyclization Cascade Reaction
Authors: Shan Zhang, Haiyang Cheng, Sheng Mo, Shiwei Yin, Zunting
Zhang, and Tao Wang
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900605
Link to VoR: http://dx.doi.org/10.1002/adsc.201900605

10.1002/adsc.201900605
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Gold(I)-Catalyzed Synthesis of Six-Membered P,O-Heterocycles
via Hydration/Intramolecular Cyclization Cascade Reaction
Shan Zhang, Haiyang Cheng, Sheng Mo, Shiwei Yin, Zunting Zhang and Tao Wang*
a
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical
Engineering, Shaanxi Normal University, No.620 West Chang'an Avenue, Xi’an 710119, China.
E-mail: chemtao@snnu.edu.cn; taowang306@hotmail.com
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
chiral cyclic phosphine oxides in good yields with high
enantioselectivities.[10]
Abstract. Herein, we report the synthesis of six-
membered P,O-heterocycles from dialkynylphosphine
oxides. By using gold(I) complexes, the chemoselectivity
of the reaction was switched from literature-reported
double hydration to a hydration/intramolecular cyclization
cascade. Control experiments indicated that the first
alkyne hydration product is an intermediate of the reaction.
In addition, a density functional theory (DFT) calculation
allowed to rationalize the observed chemoselectivity.
In contrast to other transition-metal catalysts, gold
complexes show specific catalytic activities. For
example, in our recent research on the [4 + 1]
cycloaddition of propargyl alcohols and α-diazoesters,
it was found that gold(I) catalyst promoted the reaction
via an alternative pathway to Pd(II) complexes.[11] In
2013, Gao and Xu reported the Pd(II)-catalyzed
hydration
of
alkynylphosphonates
to
β-
Keywords: Gold-catalysis; P,O-Heterocycles;
Chemoselectivity switch; Cyclization; DFT calculation
ketophosphonates. When dialkynylphosphine oxides
were subjected to the standard conditions, double
hydration products 2 were obtained (Scheme 1a).[12]
Interestingly, in our recent investigation, we found that
when gold(I) complexes were added instead of Pd(II),
the chemoselectivity of the reaction was switched from
double hydration to
a hydration/intramolecular
Homogeneous gold catalysis has become one of the
most important tools in organic synthetic toolbox.
Owing to their advantages in activation of carbon-
carbon π bonds, gold catalysts have shown their power
in the transformation of alkyne-containing
substrates.[1] For example, fruitful achievements have
been made in the gold-catalyzed rearrangement of
cyclization cascade. To continuously explore the
specific catalytic activity of gold complexes, herein we
want
to
report
a
gold(I)-catalyzed
hydration/cyclization cascade reaction for the
synthesis of six-membered P,O-heterocycles
(Scheme 1b).
3
2]
propargyl esters,[ cycloisomerizations of enynes,[3]
cyclizations of diynes,[4] oxidation of alkynes by N-
oxides[5] and transformations of propargyl alcohols
and propargyl amines.[6] Gold complexes have also
been used to promote the synthesis of heterocyclic
phosphorus compounds, which are useful in organic
synthesis, medicinal chemistry, and material science.
In 2013, Lee reported the gold(I)-catalyzed sequential
alkyne activation for the preparation of 4,6-
disubstituted phosphorus 2‑ pyrones.[7] At the same
year, the author reported the synthesis of
phosphacoumarins
via
a
gold(I)-catalyzed
hydroarylation of aryl alkynylphosphonates.[8] Very
recently, Virieux and Pirat developed a cascade
reaction to bridgehead methanophos-phocines by
Scheme 1. Literature reports and our exploration.
gold(I)-catalyzed
intramolecular
double
In our initial study, dialkynylphosphine oxide 1a
hydroarylation.[9] In 2018, Zi reported a novel chiral
gold(I)-catalyzed desymmetrization of prochiral
phenols with P‑ stereogenic centers, affording P-
was treated with AuCl3 in the presence of 1 equivalent
o
of water in DCE (1,2-dichloroethane) at 80 C for 36
h. To our delight, a six-membered P-O heterocycle 3a
1
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10.1002/adsc.201900605
Advanced Synthesis & Catalysis
Table 1. Optimization of the Reaction Conditions.[a]
Entry Catalyst
Solvent/ Time(h)
DCE/ 36h
Conversion (1a %)[b]
3a:2a[c] Yield (3a %)[d] Yield (4a %)[d]
1
AuCl3
37
7:1
21
-
2
Ph3PAuCl
AgNTf2
DCE/ 36h
-
-
-
-
3
DCE/ 36h
15
-
Trace
45
10
-
4
AuCl3/3AgNTf2
Ph3PAuNTf2
JohnPhosAuNTf2
SphosAuNTf2
IPrAuNTf2
BinapAu2(NTf2)2
IPrAuSbF6
IPrAuPF6
DCE/ 36h
59
6:1
5
DCE / 36h
DCE / 36h
DCE / 36h
DCE / 12h
DCE / 36h
DCE / 18h
DCE / 18h
DCE / 30h
DCE / 36h
DCE / 36h
DCE / 16h
DCE / 13h
CH3CN/ 24h
THF/ 36h
75
>20:1
4:1
65
-
6
92
73
-
7
91
>20:1
>20:1
8:1
88(87)
96(94)
25
-
8
100
38
-
9
-
10
11
12
13[e]
14[f]
15[g]
16[h]
17[g]
18[g]
19[g]
20[g]
21[g]
100
100
100
73
13:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
>20:1
11:1
9:1
90(84)
97(96)
96(94)
69
-
-
IPrAuOTf
IPrAuPF6
-
-
IPrAuPF6
100
100
100
100
88
97(96)
97(96)
95(95)
96(94)
79
-
IPrAuPF6
-
IPrAuPF6
-
IPrAuPF6
-
IPrAuPF6
-
IPrAuPF6
Dioxane/ 36h
DCE / 36h
Dioxane / 36h
DCE / 12h
MeOH / 12h
78
69
-
PdCl2
70
1:4
10
20
15
PdCl2
88
1:10
5
22
23
p-TSOH
p-TSOH
0
-
-
-
-
-
-
0
a) General reaction conditions: The reaction was conducted in a sealed tube under an argon atmosphere at 80 °C with 0.3
mmol of 1a, 0.3 mmol of H2O and 0.015 mmol of catalyst in 3 mL of solvent. b) The conversion of 1a was determined by 1H
1
1
NMR analysis. c) The ratio of 3a:2a was determined by H NMR analysis. d) Yield determined by H NMR analysis; the
number in parentheses represents the yields of isolated products. e) 0.009 mmol of IPrAuPF6 was added. f) The reaction was
conducted at 60 oC. g) 0.6 mmol of H2O was added. h) 1.5 mmol of H2O was added.
was obtained as a main product over double hydration
product 2a (Table 1, entry 1). Encouraged by this
result, we further optimized the reaction conditions for
the formation of 3a. Unfortunately, when Ph3PAuCl
was used as a catalyst, no conversion of 1a was
3a in 45% yield (entry 4). Fortunately, when treating
1a and water with Ph3PAuNTf2 for 36 h, 75%
conversion of 1a was achieved, affording 3a in 65%
yield with the ratio of 3a to 2a over 20:1 (entry 5). In
further optimization on gold catalysts (entries 6-7), it
was found that when IPrAuNTf2 was employed, 100%
conversion of 1a was achieved. In addition, the
reaction delivered 3a in 94% isolated yield with 3a:2a
over 20:1 ratio (entry 8). The counter anion of the
cationic gold(I) complexes was also investigated
(entries 10-12), among which -PF6 and -OTf (OTf =
observed (Table 1, entry 2). AgNTf2 (NTf2
=
bis(trifluoromethanesulfonyl)imide) was also used to
promote the reaction, which resulted in the formation
of a hydration product 4a in low yield (entry 3).
Addition of AgNTf2 in combination with AuCl3
provided an increase in reaction efficiency, affording
2
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10.1002/adsc.201900605
Advanced Synthesis & Catalysis
trifluoromethanesulfonate) gave comparative result
(96% vs 94%). Reducing the catalyst loading to 3
mol % resulted in incomplete conversion of 1a (entry
13). A longer time was needed when the reaction
temperature was decreased to 60 oC (entry 14). It was
notable that, when 2 equivalents and 5 equivalents of
water were added respectively, the yields of 3a were
not affected (entry 15-16). Polar solvents, such as
MeCN (acetonitrile), THF (tetrahydrofuran) and
dioxane (entries 17-19) were screened, among which
THF and dioxane was proved not to be suitable for the
formation of 3a. The formation of double hydration
product 2a could be promoted by the water-miscible
solvents, which admit more equivalents of water as
well as facilitate the proton transfer of hydration. [13]
PdCl2 was also examined in both DCE and dioxane.
As a result, the double hydration product 2a was
obtained as main product in both DCE and dioxane
(entries 20-21), which is in accordance with the
literature reports.[12] p-TSOH (p-toluenesulfonic acid)
was reported as an efficient catalyst for promoting the
hydration/cyclization cascade of 1,4-diyn-3-ones.[14]
However, no conversion of 1a was observed when p-
TSOH was added (entries 22-23).
After establishing the optimized conditions (Table
1, entry 15; 2 equivalent of water and 5 mol % of
IPrAuPF6 in DCE at 80 oC), we turned our attention to
the substrate scope (Scheme 2). Starting materials
bearing substituted phenyl groups were examined first,
which delivered the corresponding products 3a-3i in
good to excellent yields (81%-98%). 1-Naphthyl
group substituted product 3j was also obtained in 79%
yield. Both thiophene-2-yl-substituted product 3k and
thiophene-3-yl-substituted product 3l were obtained in
91% yield. Aliphatic starting material also worked
well, delivering the corresponding products 3m and 3n
in 92% and 88% yield, respectively. R3 group was also
evaluated. When R3 were phenyl group and tert-butyl
group, 3o and 3p were obtained in 89% and 92% yields,
respectively. When R3 was an ethoxy group, the
reaction afforded 3q in 93% yield. A product with
different R1 and R2 group (3r) was obtained in 75%
yield.
Starting
materials
bearing
two
dialkynylphosphine oxide units were also evaluated,
delivering 3s and 3t in 88% and 92% yield,
respectively. Interestingly, when 1u was subjected to
the standard condition,
a six-membered P,O-
heterocycle 3u was obtained, in which a ketone unit
was formed via the hydration of alkyne.
Besides water, amines and sodium sulfide were also
used as nucleophiles to react with dialkynylphosphine
oxide 1, giving six-membered P,N- and P,S-
heterocycles (Scheme 3). It is worth noting that, owing
to the stronger nucleophilicity of amine, the reaction
of amines with 1 could be catalyzed by silver salts. For
example, the reaction of 1a with aniline in the presence
of 10 mol % of AgNO3 afforded 5a in 88% yield. p-
Phenylenediamine was also added to react with 1a. As
a result, 90% of 5b was obtained in the presence of
IPrAuPF6 and 30% of 5b was isolated in the presence
of AgNO3, respectively. The reaction of sodium
sulfide with 1a afforded a six-membered P,S-
heterocycle 6a. In analogy to amine, the strong
nucleophilicity of sodium sulfide made this reaction
occurring in the absence of a catalyst, although the
yield is relatively lower (See SI for details).
Scheme 3. Synthesis of six-membered P,N- and P,S-
heterocycles. a) IPrAuPF6 (5 mol %) was used as a catalyst.
b) AgNO3 (10 mol %) was added as a catalyst. c) The reaction
was conducted in the absence of a catalyst.
The reduction of phosphine oxides is one of the
major methods for the synthesis of phosphines. In our
further investigation, by the use of Werner’s
method,[15] 3a was reduced by PhSiH3 in the presence
of CF3SO3H and was directly converted to 7a by
subsequent addition of BH3·THF to the reaction
mixture (eq 1).
Scheme 2. Substrate Scope. General reaction conditions:
The reaction was conducted in a sealed tube under an argon
atmosphere at 80 °C with 0.3 mmol of 1, 0.6 mmol of H2O
and 0.015 mmol of IPrAuPF6 in 3 mL of DCE for 16 h.
3
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10.1002/adsc.201900605
Advanced Synthesis & Catalysis
To gain some insights into the reaction mechanism
of the P,O-heterocycle formation, several control
experiments were conducted (Scheme 4). By addition
of D2O instead of H2O, 95% of 3a was obtained, with
P,O-heterocycle deuterated in 80% ratio (Scheme 4a).
During the optimization of the reaction conditions, 4a
was obtained as a by-product (Table 1, entry 3). We
hypothesized that 4a was the plausible intermediate for
the formation of 3a. As we expected, when 4a was
subjected to the standard condition, 3a was obtained in
96% yield within 4 min (Scheme 4b). 2a was also a
plausible intermediate to deliver 3a by an
intramolecular dehydration reaction. However, when
2a was subjected to the standard condition, no reaction
was observed (Scheme 4c).
Scheme 5. Plausible Mechanism.
In conclusion, we have reported the facile synthesis
of six-membered P,O-, P,N- and P,S-heterocycles. By
using gold(I) complexes, the chemoselectivity of the
reaction was switched from literature-reported double
hydration to a hydration/intramolecular cyclization
cascade. Control experiments indicate that ketone 4 is
the possible intermediate, which undergoes two
different pathways, resulting in the formation of
product 2 and 3. The DFT calculation provided
rationalization for the observed chemoselectivity.
Further investigation into expanding the scope of the
reaction to other nucleophiles and the application of
P,O-, P,N- and P,S-heterocycles in material science are
currently underway in our lab.
Scheme 4. Mechanistic investigation.
Based on the control experiments, a plausible
reaction mechanism is proposed by taking 1n as an
example. First, a gold(I)-catalyzed alkyne hydration
occurs, generating 4n as an intermediate.[13] In the
following, two pathways (path I and path II) result in
the formation of two products 2n and 3n. In path I, a
Experimental Section
General procedures for the gold(I)-catalyzed synthesis
of six-membered P, O-heterocycles
gold(I)-catalyzed
intramolecular
6-endo-dig
cyclization occurs via TS1, generating intermediate
Int1, which then undergoes proton shift and
protondeauration to give 3n.[16] In path II, the second
gold(I)-catalyzed alkyne hydration occurs via TS2 to
give Int3, which finally delivers double hydration
product 2n. In our study, P,O-heterocycles were
obtained in good chemoselectivity over double
hydration product. To better understand the
chemoselectivity, density functional theory (DFT)
calculations were performed.[17] To simplify the
calculation, a phenyl substituted NHC ligand was
employed (see SI for computational details). The DFT
calculation result indicates that the transition state for
the intramolecular cyclization (TS1, +10.78
kcalꢀmol−1) is lower in free energy than that for the
second alkyne hydration (TS2, +19.25 kcalꢀmol−1) by
ΔΔG*= 8.47 kcalꢀmol−1 (Scheme 5). The DFT
calculation indicates that the intramolecular
cyclization is favored over the intermolecular alkyne
hydration in the presence of a gold(I) catalyst.
IPrAuPF6 (0.015 mmol), phosphine oxide 1 (0.3 mmol), and
water (0.6 mmol) are dissolved in 3 mL of DCE in a 10 mL
sealed tube. The reaction mixture was stirred under argon at
80 oC for 16 h. Then, the solvent was removed and the crude
product was purified via column chromatography on silica
gel (methanol/dichloromethane, 1:80) to give the
corresponding product.
Acknowledgements
Financial support by the National Natural Science Foundation of
China (21502110), the Natural Science Foundation of Shaanxi
Province (2019JQ-323), the young top-notch talent of “Special
Support Plan for High-Level Talents in Shaanxi Province”, the
111 Project (B14041) and the Fundamental Research Funds for
the Central Universities (GK201903039) are greatly appreciated.
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10.1002/adsc.201900605
Advanced Synthesis & Catalysis
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5
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10.1002/adsc.201900605
Advanced Synthesis & Catalysis
COMMUNICATION
Gold(I)-Catalyzed Synthesis of Six-Membered
P,O-Heterocycles via Hydration/Intramolecular
Cyclization Cascade Reaction
Adv. Synth. Catal. Year, Volume, Page – Page
Shan Zhang, Haiyang Cheng, Sheng Mo, Shiwei
Yin, Zunting Zhang, Tao Wang *
6
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