Aryne formation via the hexadehydro Diels-Alder reaction and their Ritter-type transformations catalyzed by a cationic silver complex

Article abstract of DOI:10.1016/j.tet.2017.02.008

Despite their electrophilic nature, arynes are not known to react with nitriles under typical conditions for their formation. We demonstrated, however, that structurally diverse arynes could be generated via the hexadehydro Diels-Alder reaction and trappe

Full text of DOI:10.1016/j.tet.2017.02.008

Accepted Manuscript
Aryne formation via the hexadehydro Diels-Alder reaction and their Ritter-type
transformations catalyzed by a cationic silver complex
Sourav Ghorai, Daesung Lee
PII:
S0040-4020(17)30133-3
10.1016/j.tet.2017.02.008
TET 28449
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 24 August 2016
Revised Date: 1 February 2017
Accepted Date: 4 February 2017
Please cite this article as: Ghorai S, Lee D, Aryne formation via the hexadehydro Diels-Alder reaction
and their Ritter-type transformations catalyzed by a cationic silver complex, Tetrahedron (2017), doi:
10.1016/j.tet.2017.02.008.
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Aryne Formation via the Hexadehydro Diels-
Alder Reaction and Their Ritter-type
Transformations Catalyzed by a Cationic
Silver Complex
Leave this area blank for abstract info.
*
Sourav Ghorai and Daesung Lee
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607, USA

1
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Tetrahedron
journal homepage: www.elsevier.com
Aryne Formation via the Hexadehydro Diels-Alder Reaction and Their Ritter-type
Transformations Catalyzed by a Cationic Silver Complex
*
Sourav Ghorai and Daesung Lee
Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607, USA
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Despite their electrophilic nature, arynes are not known to react with nitriles under typical
conditions for their formation. We demonstrated, however, that structurally diverse arynes could
be generated via the hexadehydro Diels-Alder reaction and trapped with nitriles to induce the
Ritter-type reaction when catalyzed by a cationic silver species. Presumably, under these
conditions, the transiently formed aryne-silver complexes react with nitriles initially to form
nitrilium ion intermediates, which then subsequently react with either water or carboxylic acid to
yield the observed arylamides or arylimides.
Available online
Keywords:
Aryne
Aryne-silver complex
Nitrilium ion
Ritter reaction
2
016 Elsevier Ltd. All rights reserved.
1
. Introduction
Scheme 1. Aryne formation via various protocols
Arynes, as a form of transient electrophilic intermediate,
have been employed in a large number of natural product
synthesis and the development of various synthetic
1
methodologies. Despite the versatility, the effective formation
of arynes still renders a significant challenge and barrier for
further expansion of their utility in synthetic organic chemistry.
Traditionally, the 1,2-elimination of suitably functionalized
aromatic precursors has been employed for the formation of
2
arynes, many of which are pericyclic reactions in nature
(Scheme 1). Among these pericyclic processes, only one
protocol involves the de novo construction of the aromatic
framework of arynes starting from non-aromatic precursors.
Although, this particular form of pericyclic reaction was
3
discovered more than a century ago, the reactions of the
corresponding intramolecular variants pioneered by Johnson and
4
Ueda were reported since 1997. Recently, the formation of
arynes by this pericyclic reaction has been rejuvenated, and
Hoye introduced a term hexadehydro Diels-Alder reaction
5
(HDDAR) for the process.
Despite the synthetic versatility of HDDAR and its
uniqueness of forming aryne frameworks from non-aromatic
precursors, the development of this protocol still is in its infancy6
compared to the silyltriflate-based protocol of Kobayashi.
Compared to the rapid development of new aryne chemistry
based on silyltriflates and related aryne precursors, the
corresponding HDDAR-based approaches starting from non-
7
aromatic precursors are significantly underdeveloped. Thus, it is
necessary to garner information about the general reactivity
profiles of the aryne species generated via HDDAR, and expand
the suitable substrate classes.

2
Tetrahedron
ACCEPTED MANUSCRIPT
R
R
R
X
Having recognized the dearth of reports on the addition of
nitriles through their nitrogen atom with arynes or benzyne, we
N
2
H
X
9
M or
R'M
CO
2
∆
base
R
X
further explored the reaction, and reported herein are the results
of systematic investigation that leads to the development of
aryne-based new three-component coupling reactions to form
arylamides and imides. This study also demonstrated the
importance of silver species in aryne-based transformation, the
exact role of which is yet to be defined.
R
R
[
O]
F
N
SiMe
3
N
N
OTf
2
H N
hυ
∆
R
0 °C
R
2
.
Results and discussion
R
N
Our investigation commenced with optimizing reaction
O
2
S
N
Pt
N
N
conditions for symmetrical tetrayne 1 to form amide adduct 2
Table 1). In presence of silver hexafluoroantimonate as a
Ph
3
P
PPh
3
2
O S
(
catalyst (10 mol %), the reaction of tetrayne 1 in different nitrile
solvent heated at 90 °C for 5 h led to the complete consumption
In light of developing a de novo synthesis of structurally
complex pyridine derivatives, we explored the [4+2]
cycloaddition reactions between arynes generated from tetrayne
Table 1. Optimization for different amide formation
1
and oxime derivatives generated from acrolein and other enals
R1
R1
2
a
R CN
(
Scheme 2). When these reactions were carried out in
SiMe3
SiMe3
SiMe3
AgSbF6 (10 mol %)
TsN
TsN
acetonitrile as a solvent, we did not observe the expected
cycloadduct but only acetonitrile adducts in marginal yield. We
inferred that the formation of the Ritter-type product 2 is the
90 °C, 5 h
NH
R2
8
1
2
O
consequence of the initial addition of solvent nitrile with the
aryne intermediate formed from HDDAR followed by trapping
of the nitrilium ion by adventitious water contained in wet
solvent.
2
yield (%)b
entry
R CN
product
R
R
R
SiMe3
NH
1
2
3
CH3CN
TsN
TsN
TsN
72
75
56
2
a
O
O
O
Scheme 2. Diels-Alder reaction vs. solvent addition
SiMe3
NH
CN
2
2
b
c
SiMe3
NH
CN
R
SiMe3
NH
4
5
TsN
47c
CN
2
d
O
R
CN
O
69d
TsN
N
H
2
e
a
b
c
Non-distilled, used as the solvent. Isolated yiled. Yield from the reaction
d
with extra water (10 equiv). Overall yield after desilylation with TBAF.
of 1, providing the corresponding amides 2a–d. Although these
1
0
products could be obtained without the silver catalyst, lower
yields with significantly increased amount of unknown
byproducts were resulted. First, with acetonitrile, amide 2a was
obtained in 72% yield (entry 1). With propionitrile, 2b was
obtained in 75% yield (entry 2), whereas only with 24% yield of
2
was observed without the catalyst. With acrylonitrile solvent,
the reaction of 1 provided acrylamide derivative 2c in somewhat
lower 56% yield (entry 3). Although addition of extra water was
not necessary to form 2a–2c, the reaction with isobutyronitrile
required addition of water. Thus, under the same conditions with
1
0 equivalents of added water, amide 2d was generated in 47%
yield (entry 4). Aromatic nitrile behaves similarly but provided
some desilylated products. Thus, after complete removal of the

3
ACCEPTED MANUSCRIPT
silyl groups with TBAF, arylbenzamide 2e was obtained in 69%
yield (entry 5).
Table 2. Aryne-based three-component coupling for the
formation of arlyamides
The formation of single regioisomer is most likely the
consequence of the strong electronic directing effect of the silyl
substituent. The structural identity of these single regioisomeric
products was confirmed by nOe experiment.
2
a
R1
R CN
11
R1
AgSbF6 (10 mol %)
SiMe3
H2O (10 equiv)
conditions A–Eb
SiMe3
NH
R2
3
–6
7–10
O
With the successful reaction of NTs-tethered symmetrical
tetrayne 1 to generate different amide derivatives, we next
explored the reaction of other substrates containing differently
tethered tetraynes and triynes (Table 2). In general, because of
the structural variation with steric and electronic differences, all-
carbon tethered substrate 4 containing a gem-dicarboxylate and
ester-tethered triyne 5 required higher reaction temperature and
extended reaction time. For most of the reactions, addition of
water (10 equiv) significantly improved yields of the desired
product.
2
yield (%)c
entry
substrate
R CN
conditions
product
R1
12
SiMe3
NH
SiMe3
SiMe3
1
O
CH3CN
A
A
O
78
7a
3
O
R1
SiMe3
NH
2
3
CN
O
80
7
b
O
O
First, the reaction of an oxygen-tethered symmetrical tetrayne
R1
3
was carried out by heating at 90 °C for 5 h, which cleanly
SiMe3
NH
afforded acetamide 7a in 78% yield (entry 1). Similar result was
obtained when acetonitrile was replaced by propionitrile and
acrylonitrile, where propionamide 7b and acrylamide 7c were
obtained in 80% and 75% yield, respectively (entries 2 and 3). In
benzonitrile medium, arylbenzamide was generated with partial
removal of silyl group. After complete desilylation, amide 7d
was obtained in 20% overall yield (entry 4). All-carbon tethered
substrate 4 containing a gem-dicarboxylate is unreactive at 90
A
A
O
75
CN
7
c
R
CN
O
O
20d
4
5
N
H
7d
R1
(
E = CO2Me)
°
C, but at 150 °C it readily participate in the reaction with
SiMe3
SiMe3
SiMe3
E
E
E
E
acetonitrile and propionitrile to yield the corresponding amide 8a
and 8b in 59% and 30% yield (entries 5 and 6). However, with
acrylonitrile, no expected amide product was observed, probably
because of the instability of acrylonitrile at this high
temperature. It is interesting to notice the difference between the
reactions with acetonitrile and propionitrile, where addition of
CH CN
B
59
3
NH
8
a
4
O
O
R1
SiMe3
NH
E
E
CN
B
A
C
30
49
79
6
7
8
b
1
0 equivalents of water significantly improved the yield of 8a
whereas the yield of 8b was not improved by water additive. An
ynamide-tethered non-symmetrical tetrayne afforded
R1
Bu
5
O
CN
propionamide-substituted indoline 9a in 49% from the reaction
with propionitrile at 90 °C (entry 7). An ester-tethered triyne 6
derived from propiolic acid turned out to be less reactive than
tetraynes, thus the reaction was carried out at 150 °C. With
acetonitrile, the reaction of 6 provided 10a in 79% yield at 150
TsN
SiMe3
N
N
Ts
H
5
9a
0a
O
O
O
SiMe3
NH
O
CH3CN
8
9
SiMe3
1
°
1
C for 30 h (entry 8). With acrylonitrile, acrylamide derivative
0b was obtained in 46% yield after 9 h, and extended reaction
6
O
O
SiMe3
NH
time did not improve the yield (entry 9). With propionitrile, a
mixture of amides products 10c and 10c' (2.6:1) was obtained
after heating at 150 °C for 18 h (entry 10).
O
CN
CN
D
E
46
60
1
0b
O
O
With these results in hand, we envisioned that if the putative
nitrilium ion could be captured by other nucleophile rather than
water, different end products would be generated. One such
R
O
O
1
0
N
H
1
3
1
0c, R = SiMe3 (2.7:1)
0c', R = H
nucleophile is carboxylic acid. Although carboxylic acid may
complicate the reaction because they themselves are excellent
reacting counterparts with arynes, we tried to carry out the first
reaction in the presence of acetic acid. To our gratitude, the
reaction of 1 in acetonitrile and acetic acid in excess provided
the corresponding imide 11a along with amide 2a. At this point,
we assumed that by removing any adventitious water would
reduce or eliminate the formation of 2a. Indeed, addition of 4 Å
1
a
b
Non-distilled, used as the solvent. Conditions: A. 90 °C 5 h; B. 150 °C, 1.5
h; C. 150 °C, 30 h; D. 150 °C, 9 h; E. 150 °C, 18 h; Isolated yiled; Overall
yield after desilylation with TBAF.
c
d
molecular sieves to reaction improved the formation of 11a.
Optimizing the amount of acetic acid revealed that addition of 3
equivalents provided the highest yield of the desired product.
Thus, under the optimized conditions (10 mol % silver catalyst,
9
0 °C, 3 equivalents of AcOH, 10 wt % 4 Å molecular sieves)
the reaction of NTs-tethered symmetrical tetrayne 1 provided
arylimide 11a in 89% overall yield as a mixture with the

4
Tetrahedron
ACCEPTED MANUSCRIPT
corresponding desilylated product 11a' in a 10:1 ratio (entry 1).
The reaction in propionitrile afforded imide 11b and desilylated
product 11b' in 75% yield in a 5.2:1 ratio (entry 2). The same
acetonitrile and butyric acid, 11e and the corresponding
desilyated product 11b' were obtained in 45% yield with more
pronounced desilylation (entry 6). Similar to the amide forming
reaction in Table 2, the reaction of all-carbon tethered substrate
4
, although required higher reaction temperature (150 °C), full
Table 3. Aryne-based three-component coupling for the
formation of arylimides
conversion was achieved in less than 2 h. Thus, the reaction of 4
with a combination of acetonitrile and AcOH afforded 12a in
55% yield with no desilylation (entry 7). From the reaction with
propionitrile under otherwise identical conditions, 12b was
obtained in 79% yield (entry 8), and the same product was
obtained in slightly lower 68% yield by employing acetonitrile
and propionic acid (entry 9). With acrylonitrile and AcOH,
acrylimide 12c was obtained as a single product in 78% yield
2
a
R CN
R1
AgSbF6 (10 mol %)
2
SiMe3
O
R1
SiMe3
R
RCO H (3 equiv)
X
X
Y
N
R2
Y
4 Å MS (10 wt %)
conditions A or Bb
11–13
1, 4, 5
R
O
2
2
conditions
yield (%)c
entry
substrate
R CN
R CO2H
products
R1
(entry 10), and with the combination of acetonitrile and
SiMe3
SiMe3
propionic acid afforded 12d in 67% yield (entry 11). Finally,
unsymmetrical ynamide-tethered substrate 5 provided the
corresponding indolinyl imide 13a in 71% when the reaction
was carried out at 90 °C for 5 h (entry 12). With other nitrile
such as propionitrile, acrylonitrile and isobutyronitrile, the
reaction of 5 provided product 13a in reasonable yield but
contaminated with the corresponding desilylated product.
From these reactions, a general trend is noted that the
reaction with sterically more hindered carboxylic acid provided a
product in lower yield. For example, when AcOH was replaced
with propionic acid (entry 3) and butyric acid (entry 6),
significantly lower yields resulted in with more pronounced
desilylation. Another interesting observation is the formation of
products devoid of desilylation from the reaction of all-carbon
tethered substrate 4 even the reaction was carried out at 150 °C
compared to 90 °C for other substrates.
1
TsN
CH CN
CH CO H
A
O
89
d
3
3
2
TsN
SiMe3
1
0:1
N
1
11a
11b
O
R1
SiMe3
O
2
3
CN
CH3CO2H
CO2H
A
A
75
.2:1
TsN
d
5
N
O
CH3CN
54
0.91:1
d
R1
SiMe3
O
4
5
CN
CH3CO2H
CH3CO2H
A
A
TsN
TsN
87
2.6:1
d
N
O
1
1c
1d
R1
SiMe3
O
76
.7:1
CN
d
1
N
O
1
R1
TMS
O
On the basis of these results, we propose a mechanism for the
formation of amides and imides (Scheme 3). Upon heating, a
tetrayene or triyne substrate I undergoes HDDAR to form an
6
7
CH3CN
CO2H
A
B
TsN
45
0.27:1
d
N
O
1
1e
1
4
aryne species, which then forms silver-aryne complex II.
R1
(
E = CO2Me)
Formally, HDDAR is considered to be a pericyclic reaction, but
recent theoretical studies suggest that the reaction proceed in a
SiMe3
O
SiMe3
SiMe3
E
E
E
E
CH3CN
CH3CO2H
55
15
N
O
stepwise manner via radical intermediates. Once formed,
12a
4
silver-aryne complex II, although water or carboxylic acid can
be trapped to form III', under the given reaction conditions,
nitrile reacts favorably to form nitrilium species III. Trapping of
III by water or carboxylic acid would form penultimate
intermediate IV or V, respectively. Protonation of the C–Ag
bond and proton or acyl shift on IV or V will generate the
observed amide VI or imide VII. It was proved that under the
current reaction conditions, either nitrile did not converted to the
corresponding amide, nor the preformed amide reacted with the
aryne species, which supports the proposed reaction mechanism.
Although carboxylic acid is known to be a good reacting
R1
SiMe3
O
8
9
CN
CH3CO2H
CO2H
B
B
E
E
79
68
N
O
CH3CN
12b
R1
SiMe3
O
E
E
10
CN
CH3CO2H
B
B
78
67
71
N
O
1
2c
2d
R1
SiMe3
O
E
E
11
CH3CN
CO2H
13
counterpart with arynes the unique combination of their
reactivity and concentration of nitrile and carboxylic acid
ultimately provides the observed amide products.
N
O
1
R1
Bu
SiMe3
SiMe3
O
12
CH3CN
CH3CO2H
In conclusion, we developed aryne-based three-
component coupling reactions by forming structurally diverse
arynes via HDDAR of tetraynes and triynes. The facile trapping
of arynes with nitriles to induce the Ritter-type reaction is a
unique aspect of these coupling reactions. Although nitriles are
A
TsN
N
N
Ts
5
13a
O
a
b
Non-distilled, used as the solvent. Conditions: A. 90 °C, 5 h; B. 150 °C, 2
h. Isolated yiled. Ratio between the intact and the desilylated product in R .
c
d
1
Scheme 3. Mechanism for the formation of amides and imides
via the formation of arynes by HDDAR followed by their
trapping with nitriles
product 11b and 11b' were obtained from the reaction with the
combination of acetonitrile and propionic acid, but with much
lower yield (54%) with increased desilylation (entry 3). The
reaction of with acrylonitrile and AcOH yielded 11c and 11c' in
8
7% yield (entry 4). Replacing acetonitrile with more sterically
demanding isobutyronitrile slightly lower the yield (76%, 1.7:1)
and increased the extent of desilylation (entry 5). With

5
ACCEPTED MANUSCRIPT
–1
1
R'
R'
'
R
1597, 1571, 1514 cm ; H NMR (CDCl , 500 MHz): δ 7.79–
7.74 (m, 2H), 7.68 (s, 1H), 7.50 (s, 1H), 7.35–7.30 (m, 2H), 6.41
3
R
R
R
H
2
O or R'''CO
2
H
R
heat
Ag
X
X
X
(d, 1H, J = 17.0 Hz), 6.15 (dd, 1H, J = 16.5 Hz, J = 10.2 Hz),
O
II
Ag
III'
I
Ag
5.77 (d, 1H, J = 10.2 Hz), 4.60 (s, 4H), 2.41 (s, 3H), 0.46 (s,
N
C
R''
13
9
H), 0.26 (s, 9H); C NMR (CDCl , 125 MHz): δ 163.6, 143.8,
3
R'
141.7, 137.8, 137.7, 133.7, 132.4, 130.8, 129.9, 128.4, 127.6,
R'
R'
R
N
R''
H
O
R
N
R'''CO
H
R
124.5, 118.6, 105.0, 102.6, 54.4, 54.1, 21.5, 1.8, –0.4; HRMS
2
2
R
X
+
H
X
X
(
ESI) calcd for C H N O SSi [M+H] 511.1907, found
O
26 35
2
3
2
N
O
Ag
H
511.1924.
Ag
R''
Ag
O
H
R'''
IV
III
V
R'
R'
2d: This compound was obtained (Procedure A with 10 equiv
R
R
N
water additive) in 47% yield. IR (neat): 3270, 2962, 2929, 2900,
R
R
–1
1
X
X
2
148, 1662, 1597, 1569, 1506 cm ; H NMR (CDCl , 500
3
N
H
O
O
MHz): δ 7.78–7.72 (m, 2H), 7.64 (s, 1H), 7.37 (s, 1H), 7.34–7.29
(m, 2H), 4.59 (s, 4H), 2.41 (s, 3H), 2.40 (sept, 1H, J = 6.8 Hz),
H
H
O
R'''
VI
VII
1
3
1
.22 (d, 6H, J = 6.8 Hz), 0.46 (s, H), 0.25 (s, 9H); C NMR
not strong enough nucleophiles to react with arynes under
typical conditions we found that an effective reaction between
arynes and nitriles could be promoted by a cationic silver
catalyst. Presumably, under these silver-catalyzed conditions,
transiently formed aryne-silver complexes initially react with
nitriles to form nitrilium ion intermediates, which then
subsequently react with either water or carboxylic acid to yield
the observed arylamides or arylimides.
(
1
2
CDCl , 125 MHz): δ 175.4, 143.7, 142.2, 137.7, 137.3, 133.7,
3
31.9, 129.9, 127.5, 124.3, 118.5, 104.8, 102.8, 54.4, 54.1, 36.8,
1.5, 19.5, 1.9, –0.4; HRMS (ESI) calcd for C H N O SSi
2
27
39
2
3
+
[
M+H] 527.2220, found 527.2222.
2
e: This compound was obtained (Procedure A followed by
TBAF-mediated deprotection) in 69% yield. IR (neat): 3266,
2
–1
1
922, 2853, 2360, 1677, 1605, 1539, 1492 cm ; H NMR
(CDCl , 500 MHz): δ 7.96 (s, 1H), 7.86–7.81 (m, 2H), 7.79–7.75
3
(
m, 2H), 7.69 (s, 1H), 7.57–7.51 (m, 1H), 7.50–7.42 (m, 3H),
1
3
3
. Experimental section
7.35–7.30 (m, 2H), 4.62 (s, 4H), 3.25 (s, 1H), 2.41 (s, 3H); C
NMR (CDCl , 125 MHz): 165.8, 143.9, 137.9, 137.4, 135.2,
3
General procedure for preparation of arylamides (Procedure
1
1
34.3, 133.6, 132.2, 129.9, 128.9, 127.6, 127.0, 122.9, 117.6,
A): A multiyne substrate (0.1 mmol) and AgSbF (0.01 mmol)
6
15.4, 82.0, 79.8, 54.2, 53.5, 21.5; HRMS (ESI) calcd for
in nitrile (3 mL) in a Schlenk tube was flushed with nitrogen.
The mixture was stirred for 5 h at 90 °C unless otherwise noted.
Water (10 equiv) was used as additive in some cases. The
reaction mixture was concentrated, and then directly subjected to
column chromatography for purification to afford the amide
product.
–
C H N O S [M–H] 415.1116, found 415.1113.
24
19
2
3
7a: This compound was obtained (Procedure A) in 78% yield.
–
1
IR (neat): 3226, 2956, 2899, 2855, 2148, 1643, 1574, 1533 cm ;
1
H NMR (CDCl , 500 MHz): δ 7.60 (s, 1H), 7.39 (s, 1H), 5.15–
3
1
3
5.07 (m, 4H), 2.15 (s, 3H), 0.49 (s, 9H), 0.23 (s, 9H); C NMR
CDCl , 125 MHz): δ 168.5, 141.5, 141.1, 141.0, 131.9, 122.8,
(
3
General procedure for preparation of arylimides (Procedure
1
17.7, 103.8, 103.2, 74.3, 24.4, 1.8, –0.4; HRMS (ESI) calcd for
B): A multiyne substrate (0.1 mmol), AgSbF (0.01 mmol),
+
6
C H NO Si [M+H] 346.1659, found 346.1670.
18
28
2
2
AcOH (0.3 mmol), 4 Å MS (10 wt %) in nitrile (3 mL) in a
Schlenk tube was flushed with nitrogen. The mixture was stirred
for 5 h at 90 °C, unless otherwise noted. The reaction mixture
was concentrated, and then purified by flash chromatography to
afford the imide product.
7b: This compound was obtained (Procedure A) in 80% yield.
–
1
IR (neat): 3227, 2958, 2897, 2149, 1645, 1604, 1570, 1529 cm ;
1
H NMR (CDCl , 500 MHz): δ 7.67 (s, 1H), 7.36 (s, 1H), 5.13–
3
5.07 (m, 4H), 2.36 (q, 2H, J = 7.6 Hz), 1.25 (t, 3H, J = 7.6 Hz),
1
3
0
1
.49 (s, 9H), 0.23 (s, 9H); C NMR (CDCl , 125 MHz): δ 172.0,
3
4
. Characterization data
a: This compound was obtained (Procedure A) in 72% yield.
41.7, 141.0, 140.8, 131.4, 122.7, 117.4, 103.7, 103.3, 74.3,
2
74.1, 30.7, 9.6, 1.9, –0.4; HRMS (ESI) calcd for C H NO Si
19 30 2 2
+
IR (neat): 3265, 2956, 2924, 2853, 2149, 1663, 1598, 1568, 1514
[M+H] 360.1815, found 360.1808.
–1 1
cm ; H NMR (CDCl , 500 MHz): δ 7.79–7.73 (m, 3H), 7.54 (s,
3
7
c: This compound was prepared (Procedure A) in 75% yield.
1
0
1
1
H), 7.36–7.29 (m, 3H), 4.59 (s, 4H), 2.41 (s, 3H), 2.12 (s, 3H),
13
IR (neat): 3222, 2957, 2898, 2149, 1667, 1650, 1605, 1574, 1535
.46 (s, 9H), 0.25 (S, 9H); C NMR (CDCl , 125 MHz): δ
–1 1
3
cm ; H NMR (CDCl , 500 MHz): δ 7.74 (s, 1H), 7.44 (s, 1H),
3
68.4, 143.8, 141.8, 137.8, 137.7, 133.7, 132.6, 129.9, 127.6,
6
.43 (d, 1H, J = 16.8 Hz), 6.25–6.12 (m, 1H), 5.78 (d, 1H, J =
24.4, 118.9, 104.9, 102.7, 54.4, 54.1, 24.4, 21.5, 1.7, –0.4;
13
+
10.1 Hz), 5.20–5.06 (m, 4H), 0.49 (s, 9H), 0.23 (s, 9H);
C
HRMS (ESI) calcd for C H N O SSi [M+H] 499.1909, found
25
35
2
3
2
NMR (CDCl , 125 MHz): δ 163.7, 141.4, 141.1, 131.7, 131.0,
3
4
99.1928.
1
28.1, 122.8, 117.3, 103.8, 103.2, 74.3, 74.1, 1.8, –0.4; HRMS
+
2
b: This compound was obtained (Procedure A) in 75%
(ESI) calcd for C H28NO Si [M+H] 358.1659, found
19 2 2
yield. IR (neat): 3269, 2956, 2899, 2854, 2149, 1657, 1597,
358.1665.
d: This compound was obtained (Procedure A followed by
–1 1
1
2
2
0
1
1
570, 1510 cm ; H NMR (CDCl , 500 MHz): δ 7.78–7.73 (m,
H), 7.58 (s, 1H), 7.38–7.29 (m, 3H), 4.58 (s, 4H), 2.41 (s, 3H),
3
7
TBAF-mediated deprotection) in 20% yield. IR (neat): 3290,
.32 (q, 2H, J = 7.2 Hz), 1.22 (t, 3H, J = 7.4 Hz), 0.45 (s, 9H),
–1 1
13
3060, 2923, 2853, 2360, 2341, 1652, 1604, 1579, 1537 cm ; H
.25 (s, 9H); C NMR (CDCl , 125 MHz): δ 172.1, 143.8,
3
NMR (CDCl , 500 MHz): 7.88–7.84 (m, 3H), 7.75 (s, 1H), 7.59–
3
42.0, 137.7, 137.4, 133.6, 132.3, 129.9, 127.6, 124.4, 118.7,
7
.54 (m, 1H), 7.53–7.46 (m, 3H), 5.18–5.12 (m, 4H), 3.23 (s,
04.8, 102.7, 54.4, 54.1, 30.6, 21.5, 9.5, 1.8, –0.4; HRMS (ESI)
13
+
1H); C NMR (CDCl
, 125 MHz): 165.8, 140.6, 138.4, 137.6,
3
calcd for C H N O SSi [M+H] 513.2063, found 513.2068.
26
37
2
3
2
1
34.6, 132.1, 128.9, 127.0, 122.5, 116.1, 113.9, 81.1, 80.3, 74.1,
+
2
c: This compound was obtained (Procedure A) in 56%
73.4; HRMS (ESI) calcd for C H NO [M+H] 264.1025,
17 14 2
yield. IR (neat): 3246, 2956, 2924, 2853, 2148, 1661, 1625,
found 264.1021.

6
Tetrahedron
ACCEPTED MANUSCRIPT
11a: This compound was obtained (Procedure B) in 80%
–1
8
a: This compound was prepared (Procedure A, but at 150 °C
for 1.5 h with 10 equiv of water additive) in 59% yield. IR
neat): 3259, 2955, 2926, 2889, 2147, 1737, 1657, 1563, 1521
yield. IR (neat): 2956, 2899, 2852, 2150, 1708, 1597, 1567 cm ;
1
(
H NMR (CDCl , 500 MHz): δ 7.79–7.75 (m, 2H), 7.36–7.32
3
–1 1
cm ; H NMR (CDCl , 500 MHz): δ 7.56 (s, 1H), 3.76 (s, 6H),
(m, 2H), 6.77 (s, 1H), 4.67–4.60 (m, 4H), 2.43 (s, 3H), 2.22 (s,
3H), 0.33 (s, 9H), 0.26 (s, 9H); C NMR (CDCl , 125 MHz): δ
173.0, 144.3, 144.0, 141.2, 141.0, 138.6, 133.5, 130.0, 127.6,
125.8, 123.5, 106.3, 102.1, 54.1, 27.5, 21.5, 0.5, –0.4; HRMS
3
1
3
3
9
1
2
.62 (s, 2H), 3.61 (s, 2H), 2.13 (s, 3H), 0.47 (s, 9H), 0.24 (s,
H); C NMR (CDCl , 125 MHz): δ 172.0, 168.4, 141.7, 141.1,
31.6, 125.5, 125.0, 120.9, 104.0, 103.7, 59.3, 53.1, 41.1, 40.8,
4.4. 1.9, –0.3; HRMS (ESI) calcd for C H NO Si
3
1
3
3
+
(ESI) calcd for C H N O Si S [M+H]
541.2013, found
2
3
34
5
2
27 37
2
4
2
+
[
M+H] 460.1976, found 460.1975.
541.2012. 11a' (9%, obtained as an inseparable mixture with 11a
1
in a 1:1 ratio): H NMR (CDCl , 500 MHz): δ 7.80–7.75 (m,
3
8
b: This compound was prepared in 30% yield by using
2
H), 7.37–7.31 (m, 2H), 6.81 (s, 1H), 4.70–4.60 (m, 4H), 3.60
Procedure A but at 150 °C for 1.5 h. IR (neat): 3260, 2954,
13
–
1
1
(s, 1H), 2.42 (s, 3H), 2.23 (s, 6H), 0.33 (s, 9H); C NMR
CDCl , 125 MHz): δ (all peaks) 173.0, 144.3, 144.0, 141.9,
2
926, 2854, 2147, 1737, 1652, 1590, 1564, 1514 cm ; H NMR
(
3
(CDCl , 500 MHz): δ 7.62 (s, 1H), 7.26 (s, 1H), 3.76 (s, 6H),
3
1
41.5, 141.2, 141.0, 138.7, 138.6, 133.5, 133.4, 131.3, 130.0,
127.6, 125.8, 124.7, 124.0, 123.5, 123.1, 106.3, 102.1, 88.2,
1.1, 78.8, 54.2, 54.0, 53.9, 27.5, 26.9, 21.5, 0.6, 0.5, –0.4;
3
.62 (s, 2H), 3.60 (s, 2H), 2.33 (q, 2H, J = 7.4 Hz), 1.24 (t, 3H, J
13
=
7.4 Hz), 0.47 (s, 9H), 0.25 (s, 9H); C NMR (CDCl , 125
3
8
MHz): δ 172.0, 141.6, 141.4, 141.3, 131.2, 125.4, 120.7, 104.1,
03.6, 59.3, 53.1, 41.1, 40.8, 30.7, 9.6, 2.0, –0.3; HRMS (ESI)
+
HRMS (ESI) calcd for C H N O SiS [M+H] 469.1617, found
469.1620.
24
29
2
4
1
+
calcd for C H NO Si [M+H] 474.2132, found 474.2139.
24
36
5
2
1
1b: This compound was obtained (Procedure B) in 63%
9
a: This compound was obtained (Procedure A) in 49%
yield. IR (neat): 2956, 2924, 2852, 2149, 1712, 1597, 1567,
yield. IR (neat): 3295, 2955, 2929, 2871, 1666, 1609, 1593, 1544
–1
1
–1
1
1513, 1494 cm ; H NMR (CDCl
H), 7.36–7.32 (m, 2H), 6.75 (s, 1H), 4.70–4.56 (m, 4H), 2.43
s, 3H), 2.39–2.33 (m, 2H), 2.32 (s, 3H), 1.06 (t, 3H, J = 7.3 Hz),
.31 (s, 9H), 0.26 (S, 9H); C NMR (CDCl , 125 MHz): δ
176.3, 173.2, 144.0, 141.2, 141.1, 138.5, 133.5, 130.0, 127.6,
25.8, 123.6, 106.2, 102.2, 54.1, 32.4, 27.8, 21.5, 8.6, 0.5, –0.4;
HRMS (ESI) calcd for C H N O SSi [M+H] 555.2169, found
55.2151. 11b' (12%): IR (neat): 3256, 3065, 2954, 2824, 2853,
1712, 1598, 1569, 1493 cm ; H NMR (CDCl
.79–7.76 (m, 2H), 7.36–7.32 (m, 2H), 6.79 (s, 1H), 4.74–4.57
(m, 4H), 3.60 (s, 1H), 2.43 (s, 3H), 2.39–2.34 (m, 2H), 2.33 (s,
3
, 500 MHz): δ 7.79–7.75 (m,
cm ; H NMR (CDCl , 500 MHz): δ 7.72–7.68 (m, 2H), 7.49 (s,
3
2
(
0
1
2
2
1
(
1
2
H), 7.26–7.23 (m, 2H), 7.10 (S, 1H), 3.89 (t, 2H, J = 8.4 Hz),
.90 (t, 2H, J = 8.4 Hz), 2.40 (q, 2H, J = 7.8 Hz), 2.38 (s, 3H),
.36 (t, 2H, J = 7.01 Hz), 1.54–1.48 (m, 2H), 1.46–1.38 (m, 2H),
.26 (t, 3H, J = 7.6 Hz), 0.91 (t, 2H, J = 7.2 Hz); C NMR
CDCl , 125 MHz): δ 171.8, 144.3, 142.3, 137.6, 133.7, 129.8,
29.6, 127.4, 121.5, 118.1, 106.0, 94.8, 77.7, 50.0, 30.8, 30.7,
7.3, 21.9, 21.6, 19.1, 13.6, 9.6; HRMS (ESI) calcd for
C H N O S [M+H] 425.1899, found 425.1913.
13
3
13
1
3
+
28
39
2
4
2
5
–1 1
+
3
, 500 MHz): δ
24
29
2
3
7
1
0a: This compound was prepared in 79% yield by using
13
Procedure A but at 150 °C for 30 h with 10 equiv water additive.
IR (neat): 3458, 2968, 2870, 1763, 1693, 1618, 1516, 1456 cm ;
H NMR (CDCl , 500 MHz): δ 8.27 (s, 1H), 7.97 (s, 1H), 7.50
s, 1H), 5.28 (s, 2H), 2.23 (s, 3H), 0.42 (s, 9H); C NMR
3H), 1.06 (t, 3H, J = 7.2 Hz), 0.31 (s, 9H); C NMR (CDCl ,
125 MHz): δ 176.3, 173.2, 150.2, 144.0, 141.8, 141.6, 138.6,
133.4, 130.0, 127.6, 124.6, 124.1, 88.2, 81.1, 54.2, 54.0, 32.5,
27.8, 21.5, 8.6, 0.6; HRMS (ESI) calcd for C25
3
–1
1
3
13
(
(
H
31
N
2
O
4
SiS
+
CDCl , 125 MHz): δ 170.8, 168.2, 149.4, 147.2, 132.5, 131.1,
[M+H] 483.1774, found 483.1775.
3
1
21.2, 114.6, 69.4, 28.8, –0.4; HRMS (ESI) calcd for
+
11c and 11c' (inseparable mixture): A nixture of these
compounds was obtained (Procedure B) in 87% yield with a
2.6:1 ratio. IR (neat): 3254, 2956, 2924, 2900, 2854, 2150, 1703,
C H NO Si [M+ H] 264.1056, found 264.1045.
13
18
3
1
0b: This compound was prepared in 46% yield by using
1
Procedure A but at 150 °C for 9 h with 10 equiv water additive.
IR (neat): 3212, 3016, 2954, 1756, 1674, 1651, 1622, 1578, 1525
cm ; H NMR (CDCl , 500 MHz): δ 8.38 (s, 1H), 7.99 (s, 1H),
1615, 1597, 1567, 1493, 1467; (major isomer) H NMR (500
MHz, CDCl ): δ 7.80–7.75 (m, 2H), 7.37–7.33 (m, 2H), 6.76 (s,
3
–1 1
1H), 6.46–6.41 (m, 1H), 6.20–6.11 (m, 1H), 5.69–5.64 (m, 1H),
4.76–4.52 (m, 4H), 2.47 (s, 3H), 2.43 (s, 3H), 0.30 (s, 9H), 0.26
3
7
.61 (s, 1H), 6.47 (d, 1H, J = 17.0 Hz), 6.23 (dd, 1H, J = 16.9
13
Hz, J = 10.3 Hz), 5.88 (d, 1H, J = 10.4 Hz), 5.29 (s, 2H), 0.44 (s,
9
1
(s, 9H); C NMR (CDCl , 125 MHz): δ (all peaks) 173.9, 167.2,
3
13
H); C NMR (CDCl , 125 MHz): δ 170.8, 163.5, 149.5, 147.2,
144.0, 143.3, 141.9, 141.5, 141.2, 138.7, 138.6, 133.6, 131.3,
131.2, 130.0, 129.8, 127.5, 125.8, 124.7, 124.3, 123.8, 109.8,
106.3, 102.2, 88.3, 81.1, 54.1, 54.0, 27.7, 21.5, 0.6, 0.5, –0.4;
3
32.5, 130.7, 129.1, 121.3, 114.7, 69.5, –0.4; HRMS (ESI) calcd
+
for C H NO Si [M+H] 276.1056 found 276.1057.
14
18
3
+
HRMS (ESI) calcd for C H N O Si S [M+H] 553.2013, found
28
37
2
4
2
1
0c: This compound was prepared in 44% yield by using
5
53.2018.
Procedure A but 150 °C for 18 h with 10 equiv water additive.
–1
IR (neat): 3301, 2923, 2853, 1741, 1699, 1682, 1604, 1547 cm ;
11d: This compound was obtained (Procedure B) in 48%
1
H NMR (CDCl , 500 MHz): δ 8.33 (s, 1H), 7.97 (s, 1H), 7.49
yield. IR (neat): 2959, 2933, 2900, 2873, 2151, 1707, 1597, 1567
–1 1
3
(s, 1H), 5.27 (s, 2H), 2.44 (q, 3H, J = 7.5 Hz), 1.28 (t, 3H, J =
cm ; H NMR (CDCl , 500 MHz): δ 7.78–7.76 (m, 2H), 7.36–
3
13
7
1
0
.6 Hz), 0.42 (s, 9H); C NMR (CDCl , 125 MHz): δ 172.0,
7.33 (m, 2H), 6.75 (s, 1H), 4.71–4.55 (m, 4H), 2.43 (s, 3H), 2.32
(s, 3H), 2.87–2.79 (m, 1H), 2.43 (s, 3H), 2.32 (s, 3H), 1.10 (d,
3H, J = 6.7 Hz), 1.04 (d, 3H, J = 6.6 Hz), 0.32 (s, 9H), 0.26 (s,
3
70.8, 149.5, 147.4, 132.4, 130.9, 121.0, 114.4, 69.4, 31.1, 9.5, –
+
.4; HRMS (ESI) calcd for C H NO Si [M+H] 278.1212,
14
20
3
13
found 278.1222. 10c' (16%): IR (neat): 3301, 2923, 2853, 1741,
9H); C NMR (CDCl , 125 MHz): δ 180.2, 173.5, 144.1, 144.0,
3
–1
1
1
8
5
699, 1682, 1604, 1547 cm ; H NMR (CDCl , 500 MHz): δ
141.5, 141.1, 138.3, 133.6, 130.0, 127.6, 125.7, 123.5, 106.2,
3
.15 (s, 1H), 7.84 (d, 1H, J = 8.2 Hz), 7.37 (s, 1H), 7.27 (d, 1H),
.20 (s, 2H), 2.46 (q, 2H, J = 7.6 Hz), 1.28 (t, 3H, J = 7.6 Hz);
102.2, 54.1, 54.0, 35.0, 27.8, 21.5, 19.5, 19.4, 0.6, –0.4; HRMS
+
(ESI) calcd for C29
H
41
N
2
O
4
Si
S [M+H] 569.2326, found
2
13
C NMR (CDCl , 125 MHz): δ 172.5, 170.7, 148.7, 143.4,
569.2300. 11d' (28%): IR (neat): 3255, 2956, 2920, 2850, 1708,
3
–1 1
1
26.5, 120.8, 119.9, 112.2, 69.5, 30.9, 9.4; HRMS (ESI) calcd
1597 cm ; H NMR (CDCl
7.36–7.33 (m, 2H), 6.79 (s, 1H), 4.74–4.56 (m, 4H), 3.60 (s,
H), 2.87–2.80 (m, 1H), 2.43 (s, 3H), 2.32 (s, 3H), 1.11 (d, 2H, J
3
, 500 MHz): δ 7.79–7.76 (m, 2H),
+
for C H NO [M+H] 206.0817, found 206.0813.
11
12
3
1

7
ACCE
1
P
3
TED MANUSCRIPT
=
(
6.7 Hz), 1.05 (d, 2H, J = 6.8 Hz), 0.32 (s, 9H); C NMR
53.2, 41.0, 40.8, 40.7, 27.8, 17.8, 13.7, 0.7, –0.4; HRMS (ESI)
+
CDCl , 125 MHz): δ 180.2, 173.5, 144.1, 144.0, 142.0, 141.7,
calcd for C H NO Si [M+H] 530.2394, found 530.2377.
3
27 40
6
2
1
2
38.4, 130.0, 127.6, 124.6, 124.0, 88.2, 81.2, 54.2, 54.0, 35.0,
1
3a: This compound was obtained (Procedure B) in 71%
–1
7.8, 21.5, 19.5, 19.4, 0.6; HRMS (ESI) calcd for
+
yield. IR (neat): 2956, 2929, 2872, 2224, 1711, 1580, 1493 cm ;
H NMR (CDCl , 500 MHz): δ 7.69–7.65 (m, 2H), 7.29–7.25
C H N O SiS [M+H] 497.1930, found 497.1916.
1
26
33
2
4
3
1
1e: This compound was obtained (Procedure B) in 10% (in
(m, 2H), 7.21 (S, 1H), 3.91 (t, 2H, J = 8.7 Hz), 3.02 (t, 2H, J =
8.6 Hz), 2.41 (t, 2H, J = 7.0 Hz), 2.39 (s, 3H), 2.28 (s, 6H),
1.59–1.51 (m, 2H), 1.48–1.39 (m, 2H), 1.48–1.39 (m, 2H), 0.91
the table it is 45% as a total yield of the mixture) yield. IR
neat): 2958, 2927, 2901, 2872, 2850, 2152,1713, 1597 cm ; H
NMR (CDCl , 500 MHz): δ 7.80–7.76 (m, 2H), 7.36–7.32 (m,
–1 1
(
13
(m, 3H, J = 7.4 Hz), 0.29 (s, 9H); C NMR (CDCl , 125 MHz):
3
3
2
H), 6.74 (s, 1H), 4.72–4.54 (m, 4H), 2.43 (s, 3H), 2.34–2.28
δ 173.0, 144.6, 144.5, 143.6, 135.6, 134.4, 133.4, 129.9, 128.1,
(
m, 5H), 1.64–1.54 (m, 2H), 0.88 (t, 3H, J = 7.4 Hz), 0.32 (s,
127.4, 114.6, 100.8, 79.1, 49.6, 30.4, 28.1, 27.4, 22.1, 21.6, 19.3,
13
+
9
1
1
H), 0.26 (s, 9H); C NMR (CDCl , 125 MHz): δ 175.4, 173.3,
13.5, 0.7; HRMS (ESI) calcd for C H N O SSi [M+H]
3
28 37
2
4
44.0, 141.2, 141.1, 138.5, 133.6, 130.0, 127.6, 125.7, 123.6,
525.2243, found 525.2253.
06.2, 102.2, 54.1, 40.8, 27.8, 21.5, 17.7, 13.6, 0.5, –0.4; HRMS
+
(ESI) calcd for C H N O Si S [M+H]
569.2326, found
29
41
2
4
2
Acknowledgments
5
1
7
4
69.2310. 11e' (35%) IR (neat): 3261, 2958, 2929, 2873, 2853,
–1
1
712, 1597, 1493 cm ; H NMR (CDCl , 500 MHz): δ 7.80–
3
Financial support from the National Science Foundation (CHE
361620) is greatly acknowledged. We are grateful to Furong
.76 (m, 2H), 7.36–7.32 (m, 2H), 6.78 (s, 1H), 4.74–4.54 (m,
H), 3.60 (s, 1H), 2.43 (s, 3H), 2.35–2.29 (m, 5H), 1.63–1.57
1
13
Sun of the University of Illinois at Urbana-Champaignfor high
resolution mass spectrometry data.
(m, 2H), 0.89 (t, 3H, J = 7.0 Hz), 0.32 (s, 9H); C NMR (CDCl3,
1
1
2
25 MHz): δ 175.4, 173.3, 144.0, 141.8, 141.7, 138.6, 133.4,
30.0, 127.6, 124.6, 124.1, 88.2, 81.1, 54.2, 54.0, 40.8, 27.8,
1.5, 17.7, 13.6, 0.6; HRMS (ESI) calcd for C H N O SiS
26
33
2
4
+
[
M+H] 497.1930, found 497.1946.
References and notes
1
2a: This compound was obtained (Procedure B, but at 150
°
C for 2 h) in 55% yield. IR (neat): 2955, 2900, 2148, 1736,
–1
1
1
6
3
1
5
708, 1590, 1562, 1432 cm ; H NMR (CDCl , 500 MHz): δ
1. (a) Pellissier, H.; Santelli, M. Tetrahedron 2003, 59, 701–730. (b)
Wenk, H. H.; Winkler, M.; Sander, W. Angew. Chem., Int. Ed. 2003, 42,
502–528. (c) Sanz, R. Org. Prep. Proc. Int. 2008, 40, 215–291. (d)
Tadross, P. M.; Stoltz, B. M. Chem. Rev. 2012, 112, 3550–3577. (e)
Bhunia, A.; Yetra, S. R.; Biju, A. T. Chem. Soc. Rev. 2012, 41, 3140–
3152. (f) Dubrovskiy, A. V.; Markina, N. A.; Larock, R. C. Org. Biomol.
Chem. 2013, 11, 191–218. (g) Wu, C.; Shi, F. Asian J. Org. Chem. 2013,
3
.79 (s, 1H), 3.78 (s, 6H), 3.71 (s, 2H), 3.64 (s, 2H), 2.24 (s,
13
H), 0.35 (s, 9H), 0.25 (S, 9H); C NMR (CDCl , 125 MHz): δ
3
73.2, 171.8, 144.9, 143.6, 142.5, 139.6, 104.9, 103.5, 59.1,
3.2, 40.9, 40.8, 27.5, 0.6, –0.4; HRMS (ESI) calcd for
+
C H NO Si [M+H] 502.2081, found 502.2068.
25
36
6
2
2
, 116–125. (h) Yoshida, S.; Hosoya, T. Chem. Lett. 2015, 44, 1450–
1
2b: This compound was obtained (Procedure B, but at 150
1460.
°
C for 2 h) in 79% yield. IR (neat): 2955, 2901, 2149, 1736,
708, 1589, 1561 cm ; H NMR (CDCl , 500 MHz): δ 6.76 (s,
H), 3.78 (s, 6H), 3.71 (s, 2H), 3.63 (s, 2H), 2.41–2.35 (m, 2H),
.34 (s, 3H), 1.06 (t, 3H, J = 7.3 Hz), 0.33 (s, 9H), 0.25 (s, 9H);
C NMR (CDCl , 125 MHz): δ 176.6, 173.4, 171.9, 171.8,
44.8, 143.3, 142.4, 139.7, 104.8, 103.6, 59.1, 53.2, 40.9, 40.8,
2.4, 27.8, 8.6, 0.6, –0.4; HRMS (ESI) calcd for C H NO Si
2. (a) Wittig, G.; Hoffmann, R. W. Org. Synth. 1967, 47, 4. (b) Campbell,
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–1 1
1
1
2
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3
4
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13
3
1
3
[
26
38
6
2
+
M+H] 516.2238, found 516.2247.
1
2c: This compound was obtained (Procedure B, but at 150
6
62. (g) Ajaz, A.; Bradley, A. Z.; Burrell, R. C.; Li, W. H. H.; Daoust,
°
C for 2 h) in 78% yield. IR (neat): 2955, 2900, 2149, 1737,
703, 1615, 1590, 1562 cm ; H NMR (CDCl , 500 MHz): δ
.79 (s, 1H), 6.43 (dd, 1H, J = 1.6 Hz, J = 16.7 Hz), 6.19 (dd,
H, J = 10.2 Hz, J = 16.6 Hz), 5.65 (dd, 1H, J = 1.6 Hz, J = 10.3
Hz), 3.78 (s, 6H), 3.72 (s, 2H), 3.64 (s, 2H), 2.48 (s, 3H), 0.32 (s,
H), 0.25 (s, 9H); C NMR (CDCl , 125 MHz): δ 174.0, 172.0,
71.8, 167.5, 145.0, 142.6, 142.4, 140.1, 130.8, 130.3, 126.8,
25.5, 105.0, 103.5, 59.1, 53.2, 41.0, 40.8, 27.8, 0.6, –0.4;
HRMS (ESI) calcd for C H NO Si [M+H] 514.2081, found
K. J.; Bovee, L. B.; DiRico, K. J.; Johnson, R. P. J. Org. Chem. 2011,
76, 9320.
–1
1
1
6
1
3
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+
26
36
6
2
5
14.2068.
(
e) Niu, D.; Wang, T.; Woods, B. P.; Hoye, T. R. Org. Lett. 2014, 16,
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2d: This compound was obtained (Procedure B) in 67%
5
yield. In this reaction, butanoic acid was used instead of acetic
acid and the reaction mix was stirred at 150 °C for 2 h. IR
(
4
(
neat): 2957, 2901, 2875, 2854, 2149, 1737, 1710, 1589, 1562
–1 1
cm ; H NMR (CDCl , 500 MHz): δ 6.77 (s, 1H), 3.78 (s, 6H),
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3
3
1
9
1
.72 (s, 2H), 3.64 (s, 2H), 2.35 (t, 2H, J = 7.2 Hz), 2.33 (s, 3H),
.66–1.57 (m, 2H), 0.90 (t, 3H, J = 7.4 Hz), 0.34 (s, 9H), 0.26 (s,
H); C NMR (CDCl , 125 MHz): δ 175.7, 173.4, 171.9, 171.8,
13
3
5
8
45–550. (m) Pogula, V. D.; Wang, T.; Hoye, T. R. Org. Lett. 2015, 17,
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8
Tetrahedron
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