Ligand-controlled gold-catalyzed cycloisomerization of 1,: N -enyne esters toward synthesis of dihydronaphthalene

Article abstract of DOI:10.1039/c6cc03032g

We describe herein a gold-catalyzed rearrangement of propargyl esters followed by allene-ene cyclization to afford substituted bicyclic [4.4.0] dihydronaphthalene compounds. This method is also applied to vinylethers and vinylamines of 1,7-enyne esters to

Full text of DOI:10.1039/c6cc03032g

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Ligand-Controlled Gold-Catalyzed Cycloisomerization of 1,n-
Enyne Esters toward Synthesis of Dihydronaphthalene
Cite this: DOI: 10.1039/x0xx00000x
Sravan K. Thummanapelli,a Seyedmorteza Hosseyni,b Yijin Su,a Novruz G. Akhmedov,a
Xiaodong Shi*b
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/
We describe herein a gold-catalyzed rearrangement of allene intermediate A forms 8 via a propargyl ester [3,3]-
propargyl esters followed by allene-ene cyclization to afford rearrangement. Sequential [2+2] cycloaddition involving the
substituted bicyclic [4.4.0] dihydronaphtalene compounds. This allene and alkene produces a cyclobutane product.9 Later,
method is also applied to vinylethers and vinylamines of 1,7- Chen and coworkers reported several new transformations
enyne
esters
to
form
dihydroquinoline
and using this general strategy to yield 4 and 6-membered bicycles
dihydrobenzopyrane structures.
The basis of this with excellent synthetic efficiency.10 Our initial idea was to
transformation is the ligand-controlled preferential activation achieve the synthesis of aromatic bicyclic structures by
of the alkene over the allene, affording the desired aromatic modifying this scheme to favor the enyne cyclization reaction
bicyclic structures in moderate to excellent yields.
over the [2+2] cyloaddition. (Scheme 1B).
Dihydronaphthalene, 1 hydroquinoline2 and dihydrobenzo
pyrane are important building blocks in chemical and
(A) Gold catalyzed enyne-ester sequential cyclization
3
ROCO
OCOR
OCOR
R
R
•
[Au] cat.
biological research. Their syntheses are often achieved
through intramolecular cyclization. However, preparation of
these aromatic bicyclic structures has relied on C-C and C-X
bond formation strategies with limited functional group
tolerance. 4 Due to these limitations, the development of
divergent strategies to access these bicycles are of significant
interest.
R
[3,3]-rearr.
A
Ph
BzO
Ph
Et
[JohnPhosAuNCCH3]OTf 5%
DCE, 80 oC, 80%
BzO
iBu
Et
Chan ref. 8c
N
iBu
N
Ts
Ts
(B) Proposed synthesis of aromatic-bicyclic skelton and challenges
Catalysis employing gold complexes have been used in
recent years to facilitate the synthesis of complex molecules.5
One of these reactions is the gold-catalyzed cycloisomerization
of 1,n-enyes. This reaction is a hallmark method for the
efficient and atom economical single-step synthesis of complex
molecules.6 Among these reported systems, those involving an
enyne bearing a propargyl ester exhibit special reactivity.7 As
shown in Scheme 1A, upon treatment with a gold catalyst,
ROCO
O
R
OCOR
R
•
[Au]
?
R
n
n
n
A
proposed bicyclic
structure synthesis
same
[Au] cat.
n
OCOR
R
OCOR
R
Pathway I:
indene formation, ref10
Pathway II:
Allene-ene [2+2], ref 8a, 8b
a C.Eugene Bennett Department of Chemistry, West Virginia University, Morgantown,
West Virginia 26506, United States.
Scheme 1. Gold-catalyzed enyne-ester rearrangement
b Department of Chemistry, University of South Florida, Tampa, FL 33620, USA,
However, this synthetic route has not been utilized in the
past to form the desired bicyclic compounds. This is mainly
due to the possible formation of the undesirable indene
E-mail: xmshi@usf.edu
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 1

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product via a benzene addition to the Au-activated allene activation by using a sterically bulky catalyst. To explore this
intermediate (Scheme 1B).11
idea, a more stable OPiv propargyl ester 2a was prepared
Typical gold catalysts will activate both alkyne and allene (instead of OAc 2a’) and charged with 5% IPrAuNTf2 catalyst at
with approximately equal selectivity. Thus, there arises a rt. As expected, the desired cyclization product 3a was
problem of how to achieve the selective alkyne and alkene observed, albeit in low yield. Starting with this initial result,
activation in the presence of the allene intermediate.
we investigated the reaction of 1a with various gold complexes
bearing bulky primary ligands. The results are summarized in
Table 1.
Currently, our group is exploring the applications of 1,2,3-
triazoles as ligands for the formation of new transition metal
complexes. These efforts have led to the discovery of 1,2,3-
triazole gold complexes, TA-Au, that exhibit significantly
improved catalyst stability.12 One interesting discovery of the
TA-Au catalyst was its considerable chemoselectivity; the
catalyst selectively activates alkynes over allenes.13 Thus, we
postulated whether it is possible to use triazole gold catalysts
to realize the proposed transformation by selectively avoiding
allene activation. To test this hypothesis, enyne ester 1a was
prepared and charged with PPh3Au(TA)OTf (TA=benzotriazole)
catalyst. Reactions with PPh3Au(TA)OTf afforded allene 2a in
nearly quantitative yields, while those with PPh3AuNTf2 gave
exclusively the indene product 4a (Figure 1).
Table 1. Screening of reaction conditionsa,b
O
OPiv
•
nBu
nBu
PivO
3a
nBu
2a
O
[Au] cat.
OPiv
nBu
nBu
1a
4a
5a
yield (%)
Entry
cat.
temp solvent additive
2
0
27
80
42
52
0
0
0
0
3
0
11
4
75
35
0
5
20
8
0
0
1
2
3
4
5
7
8
9
5% PPh3AuNTf2
5% IPrAuNTf2
rt CH2Cl2
rt CH2Cl2
rt CH2Cl2
rt CH2Cl2
rt CH2Cl2
rt CH2Cl2
-
-
-
-
-
-
-
AcO
OAc
nBu
OAc
nBu
1% [Au]
•
nBu
5% XPhosAu(TA)OTf
5% XPhosAu(ACN)SbF6
5% tBu3PAuNTf2
0
+
48
10
65
0
23
<5
rt, DCM, 10 h
6
<5
4a'
5% di-tBuXPhosAuNTf2
5% di-tBuXPhosAuNTf2
5% di-tBuXPhosAuNTf2
1a'
2a'
rt
rt
Tol
74 trace trace
83 trace trace
89 trace trace
0%
PPh3Au(TA)OTf 1%
PPh3AuNTf2 1%
95%
0%
Tol H2O (3 eq)
10 2% di-tBuXPhosAuNTf2 50 oC Tol H2O (3 eq)
75%
PR2
iPr
iPr
iPr
Figure 1. Gold-catalyzed enyne-ester rearrangement
XPhos: R = Cy;
N
N
iPr
di-tBuXPhos: R = t-Bu
iPr
iPr
iPr
In accordance with our previous report, TA-Au exhibited
excellent chemoselectivity in the preferential activation of the
alkyne over the allene. However, this catalyst was not suitable
for alkene activation. To evaluate the reaction between the
allene and alkene, we isolated allene 2a’ and charged it with
various Lewis acids. As shown in Figure 2, typical Lewis acids,
including HOTf, Sc(OTf)3 and Bi(OTf)3, activated allene over
alkene, with no desired cyclization product 3a. Because allene
2a should theoretically possess a higher electron density than
the simple alkene, differentiation between these two
functional groups based solely on electronic effects is not
viable.
IPr
a
Reaction condition: To a solution of 1a (1 mmol) and additive in
toluene (0.2 M) catalyst was added and stirred for 12 hours. b 1H-NMR
yields by 1,3,5-trimethoxybenzene as internal standard are shown.
We started screening with PPh3AuNTf2 and it gave no desired
product 3a (entry 1). While switching the ligand to IPr gave 11% of
the desired product with 27% of the unconverted allene-ene (entry
2). XPhosAu(TA)OTf failed to activate allene-ene 2a to yield any of
the cyclization products due to the lower reactivity of catalyst
(entry 3). Gratifyingly, XPhosAu(ACN)OTf gave 48% of the desire
product 3a (entry 4). Improving on this result, using 5 mol % Di-
tBuXphosAuNTf2 formed the desired product in high yields.14 This
result is likely based on the hypothesis that a bulkier catalyst would
favour the alkene activation over the sterically-hindered allene.
Solvent screening revealed that toluene was the best solvent for
the reaction system. Additionally, using water as an additive
enhanced reaction yields. Finally, reducing the catalyst loading to 2
mol % and increasing the temperature to 50oC, afforded 89% of the
final product 3a with trace indene 4a formed. Encouraged by these
results, we explored the substrate scope of the transformation
(Table 2). Notably, OAc substrate 1a’ gave the similar reaction with
general 10-15% lower yields of the desired product 3.
O
O
OAc
nBu
cat.
nBu
nBu
2a'
CDCl3, rt
3a
3a
5a
4a
convn of
2a'
cat. = 5% IPrAuNTf2
convn of
cat.
4a
nd
5a
2% TfOH
2% Sc(OTf)3
2% Bi(OTf)3
nd
100% 0%
60%
0%
100% 0%
3a
4a
5a
2a'
20% 40%
55% 45%
73%
11%
35% 8%
Reaction of 1 with 3 equivalent D2O was performed to explore
the reaction mechanism. As expected, the fully deuterium labelled
compound 3h’ was obtained (>99% D). This result provides direct
evidence of gold promoted alkene activation as the key step in the
cyclization as discussed above. The proposed reaction mechanism
is shown in Figure 3.
Figure 2. Gold catalyzed allene-ene cycloisomerization
2
With this concern, we focused our attention on the steric
factors that may cause the two functional groups to have
different reactivity. In comparison with the alkene, the allene
moiety of 2a is more sterically hindered due to its three
substituents. Thus, it may be possible to hinder allene
2 | J. Name., 2012, 00, 1-3
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Figure 3. Plausible mechanism of the cyclization reaction.
Table 3. Extended substrate scope for hydrobenzopyranea,b
O
PivO
2% ditBuXphosAuNTf2
3 eq H2O, Tol, 50 o
R
OPiv
O
R
Piv
C
standard conditon with D2O
R
X
X
1
R
6/7
R = p-tBu-C6H4
3h'
84% yield
O
>99% 2
D
O
1
D
6a: R= nBu, 90%
6b: R= (CH2)8CH3, 86%
6c: R= Bn, 84%
D2O
R
6e, 87%
[Au]
O
R
O
OPiv
R
O
O
6d: R= (CH2)2Ph, 86%
+ O
t-Bu
Piv
•
Piv
O
O
O
[Au]
[Au]
O
O
Piv
Piv
Piv
This reaction proved to tolerate substrates bearing a wide
range of functionalities. Aliphatic linear (3a, 3b), cyclic alkynes (3c-
3e), and aromatic alkynes (3f) gave moderate to excellent yields.
Electron-donating and electron-withdrawing substituented arenes
were also tolerated (3g-3l). Most notably, thiophene-substituted
substrates gave the desired bicycle with a moderate yield (3n).
However, our methodology was not compatible with di- or tri-
substituted alkenes and internal alkenes, as desired products were
6f, 78%
6g, 82%
6h, 80%
O
O
O
Cl
N
N
N
F
Ts
Ts
Ts
7a, 72%
7b, 87%
7c, 77%
a Reaction condition: To a solution of 1a (1 mmol) and water (3 mmol) in
not formed. This result may arise from the steric hindrance of the toluene (0.2 M ditBuXPhosAuNTf2 was added and stirred for 12 hours at 50
oC. b Isolated yield.
substituted alkenes. Overall, we developed a new methodology for
the synthesis of substituted dihydronaphtalenes with good
substrate tolerability and good yields.
The functional group tolerance of our gold-catalyzed cyclization
facilitates the synthesis of substituted hydrobenzopyranes. Both
aliphatic and aromatic groups can be incorporated while sustaining
the high yield of the product (6a-6h). This expanded methodology
provided a route to hydrobenzopyranes and hydroqunolines,
valuable synthons present in a variety of natural products.
Table 2. Substrate scope of dihydronaphtalenea,b,c
O
PivO
2% ditBuXphosAuNTf2
3 eq H2O, Tol, 50 o
R
R
C
One interesting observation of this reaction was the migration
of the Piv group during formation of the final product by displacing
the carbon-gold bond. This result was synthetically valuable
because it gave us the possibility of installing different groups on
the methyl group of the pyrane ring. However, this phenomenon
did not occur when using nitrogen-containing substrates (7a-7c).
Considering that the double bonds of vinyl ethers are more
reactive due to high electron density, we questioned whether they
could be used to facilitate the formation of the 7 and 8-membered
ring. The starting materials were prepared according to literature
procedure.15 However, subjecting the substrate to the optimized
conditions (gold catalyst with 3 eq. H2O) gave significant amounts of
vinyl ether hydration product. Thus, anhydrous conditions were
used to avoid this side reaction. Under these anhydrous conditions,
the desired cyclization product 8 was observed along with a traces
amount of the [2+2] product (Figure 4). Notably, formation of 8-
membered rings gave low yield.
1
3
O
O
O
3a: R= nBu, 89%
3b: R= Bn, 64%
R
3c, 64%
O
O
3d, 79%
3e, 70%c
3f, 84%
O
O
3j, R= m-Cl, 68%
3k, R= p-Br, 73%
3l, R=o-CF3, 48%c
3g, R= p-Me, 82%
3h, R= p-tBu, 88%
3i, R= p-F, 75%
R
PivO
PivO
nBu
nBu
unsuccessful substrates, messy reactions
PivO
S
PivO
nBu
3m, 56%
nBu
O
PivO
Me/Ph
2% ditBuXphosAuNTf2
DCM, rt
R
R
a Reaction condition: To a solution of 1a (1 mmol) and water (3 mmol)
in toluene (0.2 M ditBuXPhosAuNTf2 was added and stirred for 12
hours at 50 oC. b Isolated yield. c 1H-NMR yields.
O
O
8a : R =H, 68%; 8b : R = CH3, 66%
8c : R = t-Bu, 52%; 8d : R = F, (70%, NMR yield)
Figure 4. Substrate extension to seven-membered ring systems
Encouraged by our success, we focused next on the evaluation
of substrates containing O and N heteroatoms. The corresponding
substrates were prepared and subjected to our optimized
conditions. As expected, hydrobenzopyrane 7 and hydroqunoline 8
derivatives were observed. The reaction scope is shown in Table 3.
Surprisingly, in contrast to the formation of hydrobenzopyran,
there was no Piv migration observed. While this reaction proceeds
with aromatic alkynes, the use of aliphatic alkynes resulted in
slower reactions and the formation of unidentified products.
Herein we report a chemoselective Au-catalyzed activation
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facilitated by the steric hindrance. This chemoselective activation
enabled us develop methodology to synthesize
dihydronapthalene, dihydrobenzopyrane, and hydroquinoline
derivatives with excellent functional group tolerance.
We thank the NSF (CHE-1362057) and NSFC (21228204) for
financial support.
a
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