A metal-free yne-addition/1,4-aryl migration/decarboxylation cascade reaction of alkynoates with Csp3-H centers

Article abstract of DOI:10.1039/c5ob02478a

A metal-free cascade reaction of aryl alkynoates with five different types of radical precursors (R-H) through an yne-addition/1,4-aryl migration/decarboxylation process was reported, which allowed facile and convenient access to functionalized vinyl products with "R" and protons located at the identical carbon of the formed double bond.

Full text of DOI:10.1039/c5ob02478a

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DOI: 10.1039/C5OB02478A
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Metal-free
yne-addition/1,4-aryl
migration/decarboxylation
cascade reaction of alkynoates with Csp3-H centers
De-Long Kong,a,b Liang Cheng,a Hong-Ru Wu,a,b Yang-Xiong Li,a,b Dong Wanga and Li Liu*a
Received 00th January 20xx,
Accepted 00th January 20xx
A metal-free cascade reaction of aryl alkynoates with five different types of radical precursors (R-H) through yne-
addition/1,4-aryl migration/decarboxylation process was reported, which allowed facile and convenient access to
functionalized vinyl products with “R” and proton located at the identical carbon of the formed double bond.
DOI: 10.1039/x0xx00000x
www.rsc.org/
Introduction
alkynoate, the reaction with sp3 carbon radical under either photo-
promotion or transition-metal catalysis would afford vinyl products
During the past few years, radical chemistry has played an
important role in the development of modern organic chemistry. The
synthetic methodologies based on radical species and radical
cascade reaction have been extensively investigated1 and applied in
the construction of highly complex and polycyclic molecular
frameworks.2 In particular, radical mediated sp3 C–H3 and Si–H4
activation have been demonstrated to be powerful tools for C-C and
C-Si bond formations due to the high atom-economy and low
environmental costs. The intermolecular addition of carbon- and
heteroatom-center radicals to mono- and disubstituted alkynes and
related triple bond systems also represent an extremely attractive
synthetic method.5 The fascination comes from the highly reactive
vinyl radicals generated in this step, which can be trapped by fast
cyclization or addition onto other π-systems subsequently. Although
radical addition reactions of alkynes have been well established in
the past decades, new reactions against the general principle of
addition reactions [Scheme 1, eq. (a)], that the broken two parts
separately attach to different carbon atoms of the formed double
bond, are still highly desirable.
in the mode of eq. (a).9 Inspired by recently well developed
migration/desulfonylation reactions,2 we envisioned whether the
presence of ester unit in alkynoate would trigger an aryl
migration/decarboxylation-process to give trisubstituted olefins
products by employing appropriate ‘R-H’ substrates as radical
precursors and hydrogen donors without the needs of extra
hydrogen sources [Scheme 1, eq. (b), pathway 3]. In this assumed
pathway, the process would afford the functionalized single-site-
addition vinyl products. It is worthy to note that radical aryl-
migration reactions10 and decarboxylation of vinyl carboxyl group11
have been exploited extensively, but there are very few reports on
the combination of aryl-migration with decarboxylation via ipso-
cyclized intermediate in a one pot process.
Cascade radical reactions with alkynes can show more artistic
features.6 In the case of aryl alkynoates, which are elegant radical
acceptors, two radical cascade pathways have been observed so far
[Scheme 1, eq. (b), pathway 1 and 2].7,8 Under transition-metal
catalysed conditions, reactions of aryl alkynoates with various types
of radicals (phosphoryl, trifluoromethyl, arylsulfonyl, acyl,
organoselenyl, etc.) would provide the products of cumarin
derivatives though a cascade cyclized process.7 Very recently, Li8a and
Liang8b described a Cu(I)-catalyzed functionalization of phenyl
alkynoate which afforded the dearomatic and spriocyclic products.
While, both two pathways formally gave double bonds by adding two
groups to each carbon of the tripe bonds. In the case of alkyl
Scheme 1. The addition reactions of alkynes and alkynoates
.
During the preparation of our manuscript, Han et al. reported the
oxidative difunctionalization of alkynoates with cycloalkanes as
substrates.12 Herein, we would like to report the successful execution
of our hypothesis by employing different types of ‘R-H’ substrates as
radical precursors and hydrogen donors, such as ethers, amides,
benzylic compounds etc., to react with alkynoates via yne-
a.Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory
of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy
of Sciences, Beijing 100190, China.
b.University of Chinese Academy of Sciences, Beijing 100049, China
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: See
.
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addition/1,4-aryl migration/decarboxylation cascade process under Table 1. The cascade radical addition reactions of alVkiyenwoAartticelesOwnliitnhe
metal-free conditions [Scheme 1, Eq. (b), pathway 3]. It was ethers and amides.a,b
DOI: 10.1039/C5OB02478A
particularly interesting and rare that the carbon atom, which
R· radical initially attacked, was also involved in the final hydrogen
abstraction step in a cascade process.
Results and discussion
sp3 Carbon radicals species were commonly generated by radical
initiators, thermolysis, photolysis or oxidants13. It was known that
the sp3 C–H bonds adjacent to oxygen atom could be activated
generating sp3 carbon radicals. In an initial experiment, phenyl 3-
phenylalkynoate (1a) and THF (2a) were chosen to react along with
o
DTBP (2equiv.) as the oxidant at 125 C (sealed tube) for 5 h in a
nitrogen atmosphere. Pleasingly, the aryl allyl cyclic ether 3aa could
be obtained in 85% yield in the condition. It was assumed by the
structural analysis of the product 3aa that the reaction should
undergo a radical yne-addition/1,4-aryl-migration/decarboxylation
cascade process.
Using the applicable condition, the scopes of alkynoates and other
cyclic ethers were subsequently investigated. As shown in table 1,
six-membered cyclic ethers, such as tetrahydropyran (2b) and 1,4-
dioxane (2c), which represented excellent resources of α-oxy radical,
were employed to react with 1a and the corresponding products 3ab
and 3ac were obtained in 57% and 71% yields, respectively. Reaction
with both electron-neutral and electron-deficient aryl-substituted
alkynoates smoothly afforded the desired products 3d-3f in high a Reaction conditions, for ethers: 1 (0.2 mmol), ether (2 mL), DTBP (0.4 mmol),
o
yield with 1:1 ratio of Z/E and 3g in 54% yield with 2:1 ratio of isomers. sealed tube, 125 C, 5h. For amides: 1 (0.2 mmol), amide (2 mL), DTBP (0.8
b
c
In addition, larger tert-butyl group on the para position of the phenyl mmol), 125 oC, 12h. Isolated yield. Determined by the integral area of
ring had no significant effect on the reaction (3h).
It was revealed that sp3 C–H bonds adjacent to nitrogen atom
could also be activated for the generation of sp3 carbon radicals. Thus,
1HNMR.
To display the usefulness of the reaction further, more radical
we then explored the direct synthesis of aryl allylamines compounds precursors were investigated afterwards (Table 2). Gratifyingly,
by employing amides as the radical donors in this cascade reaction. benzylic substrates were proven to be suitable for this domino
As well known, aryl allylamines motifs were frequently incorporated process via generating the benzylic primary sp3 carbon radicals. The
as an integral part of many pharmaceutically important molecules reactions of 6a-6e with 1a afforded the corresponding products 7aa-
and natural products, such as abmine-SG, abmine and naftifine, 7ae in good yield (63-80%). Next, several cycloalkanes were also
which exhibited a wide range of biological properties.14 Current employed to react with phenyl 3-phenylpropiolat 1a. As a result,
biological research15 clearly evidenced that aryl allylamines these radical reactions afforded the corresponding 1,1-
possessed high sigma (σ) receptor affinity and good σ1/σ2 selectivity. hydroalkylation-products 9 bearing five- (9ab), six- (9ab) and seven
However, arylallylamines were generally synthesized by mono or di membered (9ac) rings with moderate to excellent yield (40% - 95%).
Heck arylation of allylamines derivatives16 or by the nucleophilic However, the yield decreased dramatically when more steric bulk
addition of the appropriate aromatic anion to β-aminoketones, cyclooctane was used as the substrate, and only a trace amount of
followed by dehydration. In this section, N,N-dimetylacetamide the desired product (9ad) was detected. It is noteworthy that in
(DMA, 4a) was applied for the generation of sp3 carbon radical addition to substituted-phenyl 3-phenylpropiolates, we also tried the
adjacent to the nitrogen and the reactions of which with aryl reaction of phenyl but-2-ynoate 1b with 8b and the product 9bb of
alkynoates in the presence of DTBP (4 equiv.) at 125 oC for 12 h the tandem reaction was obtained in 55% yield.
proceeded smoothly, affording the arylallylamines products in 44-71%
Hydrosilylation of alkynes was the most straightforward method
yields (Table 1, 5c-5g). Both electron-deficient and electron-rich aryl to access vinylsilanes. However, the direct synthesis of β,β-
groups as well as the substitution patterns (ortho, meta and para) on disubstituted alkenylsilane via Si-H activation has never been
the phenyl rings of the ester of phenylynoates tolerated well in the reported before. To our delight, β,β-disubstituted alkenylsilanes
tandem reaction. Additionally, under the same conditions, cyclic could also be synthesised by this method. We employed
amide, 1-methyl-2-pyrrolidinone (4b) was applicable for the reaction representative triethylsilane as the radical precursor and the
with 1a, providing the desired product 5ab in 62% yield.
reactions of which with aryl alkynoates smoothly afforded
vinylsilanes 10a and 10b in good yield.
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t
Table 2. The cascade radical addition reactions of alkynoates with THF (Scheme 3b). The addition of BuOD (2 equiv.) to the reaction
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DOI: 10.1039/C5OB02478A
cycloalkanes, benzylic substrates, and silanes.a,b
mixtures of 1a with 8a did not lead to any deuterium-containing
products at all, thus practically ruling out the possibility that the
terminal hydrogen abstraction step of the tandem reaction might be
involved by tBuOH formed from homo-cleavage of DTBP (Scheme 3c).
In addition, two parallel reactions were carried out with THF and
THF-d8 as the substrates respectively to determine the kinetic
isotopic effect (KIE) (Scheme 3d). As a result, a kH/kD = 2.1 was
obtained.
aReaction condition: 1 (0.2 mmol), solvent (2 mL), DTBP (0.4 mmol),
sealed tube, 125 oC, 5h. For benzylic substrates and SiEt3 the
reaction time is 12 h. bIsolated yield. cDetermined by the integral
area of 1HNMR.
Interestingly, replacing phenyl with β-naphthyl on the ester unit,
less aryl migration/decarboxylation product were obtained in the
reactions of β-naphthyl 3-phenylpropenyoate with THF (2a), DMA
(4a), and cyclohexane (8a) under the standard conditions. Instead,
the reactions afforded more cyclized products. (Scheme 2).
Scheme 3. Mechanistic studies.
On the bases of the above results and literatures,4,17 the cascade
reactions were supposed to be through the attack of a sp3 C free
radical generated from hydrogen abstraction by a tert-butoxy radical
of DTBP homolysis to alkynoates, leading to yne-addition/1,4-aryl
migration/decarboxylation process. 12
Conclusions
In conclusion, we have developed an unprecedented radical
cascade reaction of alkynoates with ethers, amides, benzylic
compounds etc., which proceeds through yne-addition/1,4-aryl
migration/decarboxylation cascade process and allows facile and
convenient access to interesting single-site-addition vinyl products.
In this cascade reaction, sp3 C-H substrates act as both radical
precursors and hydrogen donors without the addition of extra
hydrogen sources. This synthetic approach represents a strategy of
Scheme 2. The reactions of β-naphthyl 3-phenylpropenyoate with
sp3 C radicals.
To elucidate the mechanism, TEMPO was employed as a radical direct decarboxylation of esters via ipso-cyclized intermediate, which
o
scavenger in the reaction of 8a with 1a at 125 C. As a result, the is especially different with the common migration/desulfonylation
formation of desired product 9aa was suppressed and the TEMPO- reactions.
Cy adduct was obtained, which provided an evidence of the
generation of cyclohexyl radical species in the reaction (Scheme 3a). Experimental section
Subsequently, deuterium-labelling experiment was conducted by
using fully deuterated THF in the reaction with 1a. It suggested that General procedure for the synthesis of 3: A mixture of alkynoate
the exclusive hydrogen source in the formed double bond was from (0.20 mmol), cyclic ethers (2 mL) and DTBP (0.4 mmol) was sealed in
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a teflon septum screw-capped tube under N2. The mixture was MHz, CDCl3) δ 145.5, 143.2, 142.5(7), 142.5(2), 141.2, 138.6, 131.8,
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stirred in an oil bath at 125 oC for 5 h. After completion of the 130.8, 130.3, 129.9, 129.7, 129.5, 129.4, 129.D2O, 1I:2180..310(239),/1C258O.B30, 2142778.A8,
reaction, the products were obtained by flash column 127.8, 127.7, 127.5, 125.3, 125.1(6), 125.1(3), 125.1, 125.0(7),
chromatography on silica gel with petroleum ether and ethyl acetate 125.0(4), 76.4, 76.3(9), 68.2(4), 68.2(1), 33.0(7), 33.0(6), 26.4(6),
as eluent.
26.4(4). HRMS (APCI): calculated C19H18F3O+ ([M+H]+): 319.1304,
2-(2,2-diphenylvinyl)tetrahydrofuran (3aa)18: Colorless oil, 43 mg, found: 319.1302. IR (KBr, cm−1) 2928, 2869, 1616, 1494, 1444, 1324,
yield 85%. 1H NMR (300 MHz, CDCl3) δ 7.37 – 7.32 (m, 3H), 7.27 - 7.20 1165, 1124, 1066, 1051, 838, 765, 701.
(m, 7H), 6.06 (d, J = 9.0 Hz, 1H), 4.33 – 4.25 (m, 1H), 3.98 – 3.91 (m, 2-(2-(2-chlorophenyl)-2-phenylvinyl)tetrahydrofuran
(3g)
：
1H), 3.77 – 3.67 (m, 1H), 2.04 – 1.97 (m, 2H), 1.91 – 1.81 (m, 1H), 1.72 Colorless oil, 31 mg, yield 54%.1H NMR (500 MHz, CDCl3) δ 7.36 (d, J
– 1.67 (m, 1H). 13C NMR (75 MHz, CDCl3) δ 143.7, 142.0, 139.4, 130.0, = 6.6 Hz, 1H), 7.28 – 7.12 (m, 13.4H), 6.18 (dd, J = 14.5, 8.9 Hz, 1H),
129.7, 128.1, 127.6, 127.4, 127.3, 76.6, 68.1, 33.1, 26.4. HRMS (APCI): 5.70 (d, J = 9.1 Hz, 1H), 4.46 (dt, J = 9.0, 7.4 Hz, 0.6H), 4.07 – 3.99 (m,
calculated C18H19O+ ([M+H]+): 251.1430, found: 251.1430. IR (KBr, 1H), 3.86 (m, 1.6H), 3.70 (m, 0.6H), 3.63 (m, 1H), 2.14 – 2.04 (m, 0.6H),
cm−1) 3056, 3023, 2969, 2867, 1599, 1492, 1444, 1205, 1151, 1049, 2.03 – 1.82 (m, 3H), 1.80 – 1.59 (m, 2.8H). 13C NMR (126 MHz, CDCl3)
764, 700.
δ 140.9, 140.7, 139.3, 138.6, 137.7, 137.1, 132.9, 132.5, 132.2, 130.9,
2-(2,2-diphenylvinyl)tetrahydro-2H-pyran (3ab)19: White solid, 30 130.5, 130.5, 130.2, 129.7, 128.9, 128.8, 128.4, 128.3, 127.8, 127.5,
mg, yield 57%, m.p. 51~52 oC. 1H NMR (400 MHz, CDCl3) δ 7.41 – 7.31 127.2, 126.8, 126.5, 126.3, 125.9, 125.4, 125.4, 125.3, 75.9, 74.9,
(m, 3H), 7.29 – 7.20 (m, 7H), 6.04 (d, J = 8.9 Hz, 1H), 4.02 – 3.93 (m, 67.1, 67.0, 32.0, 31.1, 25.4, 25.2. HRMS (APCI): calculated C18H18ClO+
1H), 3.87 – 3.78 (m, 1H), 3.36 (m, 1H), 1.80 (m, 1H), 1.68 – 1.35 (m, ([M+H]+): 285.1040, found: 285.1039. IR (KBr, cm−1) 3056, 3023, 2971,
6H). 13C NMR (101 MHz, CDCl3) δ 143.5, 142.1, 139.6, 129.8, 129.8, 2926, 2868, 1725, 1494, 1470, 1445, 1050, 761, 749, 696.
128.1, 128.0(8), 127.6, 127.4, 127.3, 75.7, 67.9, 32.3, 25.7, 23.1. 2-(2-(4-(tert-butyl)phenyl)-2-phenylvinyl)tetrahydrofuran
(3h):
1
HRMS (APCI): calculated C19H21O+ ([M+H]+): 265.1587, found: Colorless oil, 50 mg, yield 81%. H NMR (400 MHz, CDCl3) δ 7.32 –
265.1586. IR (KBr, cm−1) 3056, 3023, 2933, 2851, 1726, 1493, 1448, 7.16 (m, 6H), 7.16 – 7.03 (m, 3H), 5.98 (d, J = 9.0 Hz, 1H), 5.94 (d, J =
1444, 1202, 1082, 1032, 775, 763, 702.
9.1 Hz, 1H), 4.30 -4.24 (m, 0.5H), 4.22 -4.16 (m, 0.5H), 3.89 – 3.83 (m,
2-(2,2-diphenylvinyl)-1,4-dioxane (3ac)19: White solid, 38 mg, yield 1H), 3.70 – 3.61 (m, 1H), 2.03 – 1.86 (m, 2H), 1.86 – 1.73 (m, 1H), 1.73
71%, m.p. 89~92 oC. 1H NMR (300 MHz, CDCl3) δ 7.48 – 7.32 (m, 3H), – 1.59 (m, 1H), 1.32 – 1.21 (m, 9H).13C NMR (101 MHz, CDCl3) δ 149.4,
7.31 – 7.15 (m, 7H), 5.94 (d, J = 8.9 Hz, 1H), 4.13 (m, 1H), 3.84 – 3.60 149.1, 142.7, 142.2, 141.3, 138.5, 137.9, 135.2, 128.9, 128.6, 128.5,
(m, 5H), 3.55 – 3.44 (m, 1H). 13C NMR (75 MHz, CDCl3) δ 146.9, 141.4, 127.9, 127.0, 126.7, 126.3, 126.2, 126.1, 124.0, 123.8, 75.6, 67.0,
139.1, 129.5, 128.3, 128.2, 127.9, 127.7, 127.5, 124.1, 73.7, 70.3, 67.0, 33.5, 33.4, 32.1, 32.0(8), 30.3, 30.2, 25.5, 25.4. HRMS (APCI):
+
66.1, 66.1. HRMS (APCI): calculated C18H19O2 ([M+H]+): 267.1379, calculated C22H27O+ ([M+H]+): 307.2056, found: 307.2055. IR (KBr,
found: 267.1379. IR (KBr, cm−1) 3055, 3025, 2959, 2850, 1725, 1493, cm−1) 3055, 3027, 2963, 2867, 1734, 1512, 1493, 1444, 1363, 1268,
1445, 1117, 1090, 1050, 907, 875, 764, 701.
1050, 831, 760, 703.
2-(2-phenyl-2-(p-tolyl)vinyl)tetrahydrofuran (3d): Pale yellow solid, General procedure for the synthesis of 5: A mixture of alkynoate
38 mg, yield 72%, m.p. 46~48 oC. 1H NMR (300 MHz, CDCl3) δ 7.36 – (0.20 mmol), amide (2 mL) and DTBP (0.8 mmol) was sealed in a
7.06 (m, 9H), 6.03 (d, J = 9.0 Hz, 1H), 4.35 – 4.24 (m, 1H), 3.98 – 3.90 teflon septum screw-capped tube under N2. The mixture was stirred
(m, 1H), 3.76 – 3.69 (m, 1H), 2.38(s, 1.5H), 2.32 (s, 1.5H), 2.04 – 1.97 in an oil bath at 125 oC for 12 h. After completion of the reaction, the
(m, 2H), 1.90 – 1.85 (m, 1H), 1.77 – 1.68 (m, 1H). 13C NMR (75 MHz, products were obtained by flash column chromatography on silica
CDCl3) δ 143.7, 143.6, 142.3, 139.6, 139.2, 137.2, 137.0, 136.5, 130.0, gel with petroleum ether and ethyl acetate as eluent.
129.9, 129.5, 128.9, 128.8(7), 128.8(2), 128.0, 127.7, 127.5, 127.4, N-(3,3-diphenylallyl)-N-methylacetamide (5aa): Pale yellow oil, 32
127.3, 76.7, 68.1, 33.1, 26.4, 21.3, 21.1. HRMS (APCI) calculated mg, yield 61%. 1H NMR (300 MHz, CDCl3) δ 7.41 – 7.14(m, 10H), 6.03
C19H21O+ ([M+H]+): 265.1587 found: 265.1586. IR (KBr, cm−1) 3052, (q, J = 6.8 Hz, 1H), 4.09 (d, J = 6.9 Hz, 1H), 3.96 (d, J = 6.6 Hz, 1H), 2.90
3022, 2970, 2921, 1653, 1633, 1511, 1444, 1050,818, 765, 700.
(m, 3H), 2.13 – 1.96 (m, 3H). 13C NMR (75 MHz, CDCl3) δ 170.5, 145.3,
2-(2-(4-iodophenyl)-2-phenylvinyl)tetrahydrofuran (3e)： Colorless 144.9, 141., 141.1, 139.0, 138.6, 129.7, 129.6, 128.5, 128.3(7),
oil, 62 mg, yield 90%. 1H NMR (500 MHz, CDCl3) δ 7.70 (d, J = 7.8 Hz, 128.3(3), 128.2, 127.9, 127.5, 127.4, 127.3, 127.2, 124.3, 123.1, 49.8,
1H), 7.59 (d, J = 7.9 Hz, 1H), 7.44 – 7.17 (m, 5H), 7.07 – 6.92 (m, 2H), 46.1, 35.5, 33.2, 21.8, 21.4. HRMS (ESI): calculated C18H19ONNa+
6.05 (dd, J = 8.5, 4.7 Hz, 1H), 4.25 (M, 1H), 3.94 M, 1H), 3.76-3.72 (m, ([M+Na]+): 288.1358, found: 288.1355. IR (KBr, cm−1) 3055, 3023,
1H), 2.05 -1.98 (m, 2H), 1.95 – 1.83 (m, 1H), 1.79 – 1.68 (m, 1H). 13
C
2922, 2851, 1647, 1493, 1444, 1139, 1018, 763, 702.
NMR (126 MHz, CDCl3) δ 141.7, 140.5, 140.4, 137.9, 137.7, 136.2, 5-(2,2-diphenylvinyl)-1-methylpyrrolidin-2-one (5ab): Colorless oil,
1
136.2, 130.9, 129.3, 129.2, 128.9, 128.4, 127.3, 127.2, 126.6, 126.5, 34 mg, yield 62%. H NMR (300 MHz, CDCl3) δ 7.49 – 7.13 (m, 10H),
92.1, 92.1, 75.5, 75.4, 67.1, 32.0, 32.0, 25.4. HRMS (APCI): calculated 5.93 (d, J = 9.8 Hz, 1H), 4.09 (m, 1H), 2.75 (s, 3H), 2.45 (m, 1H), 2.33
C18H18IO+ ([M+H]+): 377.0396, found: 377.0395. IR (KBr, cm−1) 3056, (m, 1H), 2.21 (m, 1H), 1.87 (m, 1H). 13C NMR (75 MHz, CDCl3) δ 174.8,
3022, 2965, 2868, 1725, 1493, 1049, 1006, 1014, 821, 745, 701.
2-(2-phenyl-2-(4-(trifluoromethyl)phenyl)vinyl)tetrahydrofuran
(3f): Colorless oil, 52 mg, yield 82%. 1H NMR (500 MHz, CDCl3) δ 7.63 300.1358, found: 300.1356. IR (KBr, cm−1) 3055, 2921, 2686, 1492,
(d, J = 8.0 Hz, 1H), 7.52 (d, J = 8.2 Hz, 1H), 7.42 – 7.32 (m, 4H), 7.31 – 1444, 1393, 1266, 1113, 1074, 1029, 766, 702.
145.6, 141.0, 138.8, 129.5, 128.5, 128.4, 128.3, 128.0, 127.7, 127.3,
58.9, 30.2, 27.9, 25.8. HRMS (ESI): calculated C19H19ONNa+ ([M+Na]+):
7.25 (m, 2H), 7.23 – 7.17 (m, 2H), 6.12 (m, 1H), 4.33-3.30 (m, 1H), N-(3-(2-chlorophenyl)-3-phenylallyl)-N-methylacetamide (5c): Pale
4.26 – 4.19 (m, 1H), 3.96-3.92 (m, 1H), 3.79 – 3.71 (m, 1H), 2.10 – yellow oil, 28 mg, yield 44%.1H NMR (500 MHz, CDCl3) δ 7.54– 7.12
1.96 (m, 2H), 1.93 – 1.84 (m, 1H), 1.80 – 1.70 (m, 1H). 13C NMR (126 (m, 13H), 6.19 (m, 1H), 5.71 (m, 0.5H), 4.30 (d, J = 6.6 Hz, 0.5H), 4.22
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– 4.10 (m, 1H), 3.87 (m, 0.5H), 3.82 – 3.68 (m, 1H), 2.96 – 2.90 (m, 121.7, 121.6, 49.8, 46.3, 46.2, 35.6, 33.4, 29.71, 21.78, 21.4, 21.3.
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+
4.5H), 2.05 (dd, J = 39.8, 13.5 Hz, 4.5H). 13C NMR (126 MHz, CDCl3) δ HRMS (ESI): calculated C18H19ONBr+ ([M+H] ): 344.0644, found:
DOI: 10.1039/C5OB02478A
170.6, 143.1, 142.6, 142.0, 141.8, 141.7, 141.2, 139.4, 139.1, 138.4, 344.0640. IR (KBr, cm−1) 3024, 2923, 2852, 1734, 1644, 1485, 1399,
138.0, 137.6, 137.2, 133.7, 133.6, 133.0, 131.6, 131.3, 131.2, 131.1, 1366, 1260, 1071, 1010, 823, 767, 703.
130.0(5), 130.0, 129.8(7), 129.8(5), 129.5, 129.4, 129.3, 129.1(2), General procedure for the synthesis of 7 and 9: A mixture of phenyl
129.1, 129.0, 128.9, 128.6, 128.5, 128.3, 128.2, 128.1, 128.0, 127.8, alkynoate (1a, 0.20 mmol), alkanes (2a, 4 mL) and DTBP (0.4 mmol)
127.6, 127.4, 127.0, 126.9, 126.6, 126.5, 126.4, 126.3, 125.6, 124.7, was sealed in a teflon septum screw-capped tube under N2. The
115.4, 49.9, 49.4, 46.3, 45.5, 35.8, 35.5, 33.4, 33.5, 21.8, 21.7, 21.4, mixture was stirred in an oil bath at 125 oC. After completion of the
21.3. HRMS (ESI): calculated C18H18ONClNa+ ([M+Na]+): 322.0969, reaction, the desired products were obtained by flash column
found: 322.0965. IR (KBr, cm−1) 3055, 3022, 2922, 2851, 1724, 1651, chromatography on silica gel with petroleum ether as eluent.
1494, 1401, 1261, 1140, 1033, 759, 696.
prop-1-ene-1,1,3-triyltribenzene (7aa)18: Colorless oil, 40 mg, yield
N-methyl-N-(3-phenyl-3-(m-tolyl)allyl)acetamide (5d): Pale yellow 77%. 1H NMR (500 MHz, CDCl3) δ7.40 - 7.19(m, 15H), 6.26 (t, J = 7.6
oil, 32 mg, yield 57%. 1H NMR (500 MHz, CDCl3) δ 7.48 – 6.95 (m, 9H), Hz, 1H), 3.46 (d, J = 7.6 Hz, 2H). 13C NMR (126 MHz, CDCl3) δ 142.6,
6.08 – 5.95 (m, 1H), 4.15 – 4.02 (m, 1H), 3.95 (dd, J = 6.5, 4.5 Hz, 1H), 142.5, 141.0, 139.8, 129.9, 128.5, 128.4, 128.3, 128.1, 127.8, 127.4,
2.96 – 2.84 (m, 3H), 2.36 - 2.31 (m, 3H), 2.08 - 1.98 (d, 3H). 13C NMR 127.2, 127.1, 126.0, 35.9. HRMS (APCI): calculated C21H19+ ([M+H]+):
(126 MHz, CDCl3) δ 170.5, 170.4, 145.4, 145.0, 144.9, 141.6, 141.5, 271.1481, found: 271.1482. IR (KBr, cm−1) 3080, 3053, 3020, 2921,
141.2, 141.1, 139.1, 138.9, 138.7, 138.6, 138.2, 137.9, 137.7, 130.9, 2852, 2246, 1598, 1513, 1494, 1443, 1073, 1030, 910, 763, 700.
130.4, 130.1, 129.7, 129.6, 128.8, 128.6, 128.5, 128.4, 128.3, 128.3(4), (3-(o-tolyl)prop-1-ene-1,1-diyl)dibenzene (7ab)20: Colorless oil, 34
128.3(1), 128.2, 128.1, 128.0, 127.9, 127.8, 127.5, 127.4, 127.3, 127.2, mg, yield 63%. 1H NMR (500 MHz, CDCl3) δ 7.42 – 7.11 (m, 14H), 6.19
126.8, 126.7, 124.7, 124.5, 124.3, 124.2, 123.1, 49.8(4), 49.8(0), 46.1, (t, J = 7.4 Hz, 1H), 3.43 (d, J = 7.4 Hz, 2H), 2.19 (s, 3H). 13C NMR (126
46.0, 35.5, 33.2, 33.2, 29.7, 22.7, 21.8, 21.4(4), 21.4(2), 21.3. HRMS MHz, CDCl3) δ 142.5, 139.9, 139.3, 136.3, 130.1, 129.9, 128.6, 128.3,
(ESI): calculated C19H21ONNa+ ([M+Na]+): 302.1515, found: 302.1511. 128.1, 127.4, 127.2, 127.0, 126.2, 126.0, 33.8, 19.5. HRMS (APCI):
IR (KBr, cm−1) 3022, 2924, 2854, 1734, 1651, 1601, 1492, 1444, 1401, calculated C22H21+ ([M+H]+): 285.1637, found: 285.1639. IR (KBr, cm−1)
1258, 1137, 1020, 787, 765, 701.
3055, 3020, 2920, 2850, 1494, 1443, 1030, 741, 700.
N-methyl-N-(3-phenyl-3-(p-tolyl)allyl)acetamide (5e): Pale yellow (3-(m-tolyl)prop-1-ene-1,1-diyl)dibenzene (7ac)18: Colorless oil, 45
oil, 36 mg, yield 66%. 1H NMR (400 MHz, CDCl3) δ 7.44 – 7.03 (m, 9H), mg, yield 80%. H NMR (500 MHz, CDCl3) δ 7.39 (t, J = 7.4 Hz, 2H),
1
6.04 – 5.95 (m, 1H), 4.08 (m, 1H), 3.95 (m, 1H), 2.90 - 2.87 (m, 3H), 7.32 (t, J = 7.3 Hz, 1H), 7.28 – 7.20 (m, 7H), 7.18 (dd, J = 10.2, 5.2 Hz,
2.40 - 2.32 (m, 3H), 2.08 - 1.98 (m, 3H). 13C NMR (101 MHz, CDCl3) δ 1H), 7.00 (t, J = 7.0 Hz, 3H), 6.26 (t, J = 7.6 Hz, 1H), 3.43 (d, J = 7.6 Hz,
170.3, 145.2, 145.1, 144.8, 144.7, 141.7, 141.4, 139.2, 138.7, 138.3, 2H), 2.33 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 141.4, 141.3, 139.8,
137., 137.6, 137.3, 137.1, 136.0, 135.6, 129.8, 129.7, 129.6, 129.5, 138.8, 137.0, 128.9, 128.2, 127.3, 127.2, 127.1, 126.9, 126.3, 126.1,
+
129.2, 129.0, 128.9, 128.5, 128.3, 128.2, 128.1, 127.8, 127.4, 127.3(8), 126.0, 125.7, 124.4, 34.8, 20.4. HRMS (APCI): calculated C22H21
127.3, 127.2, 127.1, 124.2, 123.4, 123.0, 122.3, 49.8, 49.7(8), 46.1, ([M+H]+): 285.1637, found: 285.1639. IR (KBr, cm−1) 3055, 3021, 2922,
46.0, 35.5, 33.2(6), 33.2, 21.8, 21.4, 21.3, 21.1. HRMS (ESI): calculated 2850, 1600, 1494, 1443, 1030, 771, 700.
C19H21ONNa+ ([M+Na]+): 302.1515, found: 302.1511. IR (KBr, cm−1) (3-(p-tolyl)prop-1-ene-1,1-diyl)dibenzene (7ad)18: Colorless oil, 39
1
3023, 2921, 2851, 1651, 1510, 1491, 1137, 1019, 818, 765, 701.
mg, yield 71%. H NMR (500 MHz, CDCl3) δ 7.38 (t, J = 7.6 Hz, 2H),
N-(3-(4-fluorophenyl)-3-phenylallyl)-N-methylacetamide
(5f): 7.34 – 7.29 (m, 1H), 7.27 – 7.19 (m, 7H), 7.12 – 7.06 (m, 4H), 6.25 (t,
Colorless oil, 40 mg, yield 71%. H NMR (500 MHz, CDCl3) δ 7.45 – J = 7.8 Hz, 1H), 3.43 (d, J = 7.6 Hz, 2H), 2.32 (s, 3H). 13C NMR (126 MHz,
7.27 (m, 3H), 7.24 – 7.05 (m, 5H), 7.01 – 6.92 (m, 1H), 6.07 – 5.93 (m, CDCl3) δ 142.5, 142.3, 139.9, 137.9, 135.5, 130.0, 129.2, 128.3, 128.3,
1H), 4.12 – 4.04 (m, 1H), 3.95 (dd, J = 6.6, 3.6 Hz, 1H), 2.90 (m, 3H), 128.1, 128.1, 127.34, 127.1, 127.0, 35.5, 21.0. HRMS (APCI):
2.11 - 2.00 (m, 3H). 13C NMR (126 MHz, CDCl3) δ 170.8, 163.5, 163.3, calculated C22H21+ ([M+H]+): 285.1637, found: 285.1639. IR (KBr, cm−1)
163.1, 161.6, 161.3, 161.2, 144.4, 143.9, 141.3, 140.9, 138.8, 138.4, 3058, 3025, 2920, 2850, 1494, 1452, 1443, 1073, 1030, 760, 697.
1
137.6, 137.5, 137.2(4), 137.2(1), 134.8, 134.4, 131.5, 131.4, 131.3(5), (3-(3,5-dimethylphenyl)prop-1-ene-1,1-diyl)dibenzene
(7ae)18:
131.3, 129.6, 129.5(6), 129.5(1), 129.1, 129.0, 128.9, 128.8, 128.6, Colorless oil, 42 mg, yield 75%. 1H NMR (500 MHz, CDCl3) δ 7.31 (t, J
128.5, 128.4, 128.2, 128.1, 128.0, 127.7, 127.6, 127.4, 127.2, 124.5, = 7.4 Hz, 2H), 7.24 (t, J = 7.4 Hz, 1H), 7.16 (dt, J = 16.5, 4.4 Hz, 7H),
123.9, 123.4, 122.8, 120.3, 115.7, 115.5, 115.4(7), 115.4, 115.3, 6.80 – 6.70 (m, 3H), 6.18 (t, J = 7.6 Hz, 1H), 3.32 (d, J = 7.6 Hz, 2H),
115.1(4), 115.1(1), 114.9, 49.8, 46.3, 46.2, 35.6, 33.4, 33.3, 21.8, 2.21 (s, 6H). 13C NMR (126 MHz, CDCl3) δ 142.5, 142.2, 140.9, 139.9,
21.3(6), 21.3(4). HRMS (ESI): calculated C18H18ONFNa+ 138.0, 130.0, 128.3, 128.1(2), 128.1, 127.7, 127.4, 127.1, 127.0, 126.2,
+
([M+Na]+):306.1264, found: 306.1260. IR (KBr, cm−1) 3055, 2920, 35.8, 21.3. HRMS (APCI): calculated C23H23 ([M+H]+): 299.1795,
2850, 1644, 1601, 1507, 1402, 1223, 1159, 1016, 836, 765, 700.
found: 299.1795. IR (KBr, cm−1) 3054, 3019, 2918, 2851, 1602, 1494,
N-(3-(4-bromophenyl)-3-phenylallyl)-N-methylacetamide (5g): Pale 1443, 1073, 1030, 845, 760, 700.
yellow oil, 44 mg, yield 69%.1H NMR (400 MHz, CDCl3) δ 7.54 (m, 1H), (2-cyclopentylethene-1,1-diyl)dibenzene (9aa)18: Colorless oil, 20
7.47 – 7.24 (m, 4H), 7.23 – 7.01 (m, 4H), 6.09 – 5.96 (m, 1H), 4.07 (dd, mg, yield 40%. 1H NMR (500 MHz, CDCl3) δ 7.29 -7.21 (m, 3H), 7.20 –
J = 6.8, 2.4 Hz, 1H), 3.95 (d, J = 6.6 Hz, 1H), 2.89 (m, 3H), 2.11 - 2.00 7.10 (m, 7H), 5.90 (d, J = 10.0 Hz, 1H), 2.50 – 2.40 (m, 1H), 1.76 – 1.66
(m, 3H).13C NMR (101 MHz, CDCl3) δ 170.8, 144.4, 144.3, 143.9, 143.8, (m, 2H), 1.64 -1.57(m, 2H), 1.48 – 1.39 (m, 2H), 1.35 -1.28 (m, 2H).
140.9, 140.6, 140.4, 140.0, 138.4, 138.0, 137.9, 137.5, 131.8, 131.6, 13C NMR (126 MHz, CDCl3) δ 141.8, 139.5, 138.9, 134.4, 128.9,
131.5, 131.3, 129.7, 129.5, 128.9, 128.8, 128.7, 128.5, 128.4, 128.3, 127.0(3), 127.0, 126.2, 125.74, 125.6, 39.4, 33.2, 24.5. HRMS (APCI):
128.1, 127.7, 127.7, 127.3, 127.2, 124.7, 123.6, 123.5, 122.1, 122.0,
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calculated C19H21+ ([M+H]+): 249.1637; found: 249.1639. IR (KBr, cm−1) C23H19O3+ ([M+H]+): 343.1328, found: 343.1321. IR (KBr, cm−1) 2949,
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DOI: 10.1039/C5OB02478A
3055, 3021, 2952, 2860, 1598, 1494, 1444, 1073, 1030, 801, 762, 699. 1724, 1588, 1556, 1468, 1347, 1101, 1055, 1020, 932, 818, 774, 703.
2-cyclohexylethene-1,1-diyl)dibenzene (9ab)3c: Colorless oil, 50 mg, N-methyl-N-((2-oxo-4-phenyl-2H-benzo[g]chromen-3-yl) methyl)
1
yield 95%. H NMR (300 MHz, CDCl3) δ 7.35-7.29 (m, 3H), 7.23-7.16 acetamide (13b): Pale yellow oil, 48 mg, yield 63%. 1H NMR (500 MHz,
(m, 7H), 5.90 (d, J = 9.9 Hz, 1H), 2.25-2.04 (m, 1H), 1.55-1.70 (m, 5H), CDCl3) δ 8.61 (m, 1H), 7.84 (m, 1H), 7.71 – 7.49 (m, 6H), 7.39 – 7.32
1.20-1.22 (m, 5H); 13C NMR (75 MHz, CDCl3) δ 142.9, 140.6, 139.6, (m, 1H), 7.29 – 7.27 (m, 1H), 6.98 (m, 1H), 4.40 (d, 2H), 2.99 - 2.74 (m,
136.0, 130.0, 128.1, 128.0, 127.2, 126.8, 126.7, 38.4, 33.4, 26.0, 25.6; 3H), 1.89 (m, 3H). 13C NMR (126 MHz, CDCl3) δ 170.9, 170.4, 161.4,
+
HRMS (APCI): calculated C20H23 ([M+H]+): 263.1794; found: 161.2, 155.9, 154.4, 150.4, 149.9, 134.8, 134.5, 134.1, 133.8, 129.4,
263.1798. IR (KBr, cm−1) 3080, 3056, 3021, 2922, 2850, 1632, 1579, 129.3, 129.1, 128.9, 128.7, 128.6, 128.3, 128.1, 127.7, 127.6, 127.4,
1495, 1445, 1073, 969, 898, 761, 700.
127.1, 124.2, 123.9, 123.0, 122.9(2), 122.9, 122.8, 122.6, 122.5, 121.1,
(2,2-diphenylvinyl)cycloheptane (9ac): Colorless oil, 30 mg, yield 120.0, 115.7, 115.4, 46.6, 45.6, 37.1, 31.3, 21.7, 21.1. HRMS (ESI):
55%. 1H NMR (400 MHz, CDCl3) δ 7.40 – 7.33 (m, 2H), 7.33 – 7.27 (m, calculated C23H20O3N+ ([M+H]+): 358.1437, found: 358.1430. IR (KBr,
1H), 7.21 (m, 7H), 6.01 (d, J = 10.3 Hz, 1H), 2.31 (m, J = 13.4, 8.9, 4.5 cm−1) 3051, 2926, 2853, 1720, 1643, 1590, 1559, 1468, 1399, 1352,
Hz, 1H), 1.80 – 1.67 (m, 2H), 1.68 – 1.57 (m, 2H), 1.53 – 1.32 (m, 8H). 1102, 1072, 1021, 819, 799, 755, 705.
13C NMR (101 MHz, CDCl3) δ 143.0, 140.6, 138.1, 136.6, 129.8, 128.1, 3-cyclohexyl-4-phenyl-2H-benzo[g]chromen-2-one (14b): White
o
1
128.0, 127.2, 126.7, 126.6, 45.6, 35.0, 28.6, 26.2. HRMS (APCI): solid. Yield 40%, m.p. 186~189 C. H NMR (500 MHz, CDCl3) δ 8.59
calculated C21H25+ ([M+H]+): 277.1950; found: 277.1951. IR (KBr, cm−1) (d, J = 8.1 Hz, 1H), 7.81 – 7.79 (m, 1H), 7.66 – 7.45 (m, 6H), 7.24 (dd,
3079, 3055, 3021, 2922, 2851, 1597, 1494, 1457, 1443, 1072, 761, J = 7.8, 1.4 Hz, 2H), 6.88 (d, J = 8.8 Hz, 1H), 2.47 – 2.35 (m, 1H), 2.20
700.
(m, 2H), 1.72 (d, 2H), 1.55 – 1.49 (m, 2H), 1.28 (m, 2H), 1.08 – 0.99
(1-cyclohexylprop-1-en-2-yl)benzene (9bb)21: Colorless oil, 22 mg, (m, 2H). 13C NMR (126 MHz, CDCl3) δ 160.3, 151.3, 149.3, 135.8,
yield 56%. 1H NMR (300 MHz, CDCl3) δ 7.46 – 7.14 (m, 5H), 5.63 (dd, 134.0, 130.52, 128.8, 128.4, 128.2, 128.0, 127.5, 126.9, 123.4, 123.3,
J = 9.0, 1.1 Hz, 0.5H), 5.27 (dd, J = 10.0, 1.2 Hz, 0.5H), 2.45 – 2.17 (m, 122.9, 122.4, 116.0, 41.2, 29.2, 26.5, 25.5. HRMS (ESI): calculated
1H), 2.03 (dd, J = 14.7, 1.3 Hz, 3H), 1.87 1.03 (m, 11H). 13C NMR (75 C25H23O2+ ([M+H]+): 355.1692, found: 355.1685. IR (KBr, cm−1) 2922,
MHz, CDCl3) δ 144.0, 142.6, 134.6, 134.2, 134.0, 132.7, 128.9, 128.1, 2851, 1718, 1632, 1588, 1553, 1504, 1469, 1449, 1351, 1101,
128.0, 127.9, 127.8, 126.4, 126.3, 125.6, 122.9, 37.7, 37.3, 33.6, 33.0, 1067,966, 817,791, 774, 743, 714, 701.
31.9, 29.7, 26.7, 26.1, 26.0, 25.8, 25.7, 15.8. HRMS (EI): calculated 2-(2-cyclohexyl-1-phenylvinyl)naphthalene (14a): Colorless oil.
1
C15H20: 200.1565; found: 200.1561. IR (KBr, cm−1) 3056, 3022, 2922, Yield 23%. H NMR (500 MHz, CDCl3) δ 7.89 – 7.65 (m, 3H), 7.52 –
2850, 1659, 1633, 1447, 1260, 1025, 802, 756, 699.
7.32 (m, 4H), 7.28 (d, J = 8.4 Hz, 1H), 7.25 – 7.18 (m, 3H), 6.02 (dd, J
General procedure for the synthesis of 10: A mixture of alkynoate = 24.9, 10.0 Hz, 1H), 2.25 – 2.16 (m, 1H), 1.69 (m, 4H), 1.27 – 1.06 (m,
(0.10 mmol), silane (2 mL) and DTBP (0.4 mmol) was sealed in a teflon 6H). 13C NMR (126 MHz, CDCl3) δ 142.8, 140.5, 140.3, 139.6, 139.5,
septum screw-capped tube under N2. The mixture was stirred in an 138.1, 136.6, 136.4, 133.3, 132.4, 132.4, 129.9, 128.4, 128.3, 128.2,
oil bath at 125 oC for 12 h. After completion of the reaction, the 128.1, 128.0, 127.7, 127.5, 127.5, 127.3, 126.8, 126.8, 126.2, 125.9,
products were obtained by flash column chromatography on silica 125.9, 125.7, 125.5, 125.4, 38.4, 38.3, 33.3, 26.0, 25.9, 25.6, 25.5
+
gel with petroleum as eluent.
C24H25 ([M+H]+): 312.1956, found: 312.1960. IR (KBr, cm−1) 3054,
(2,2-diphenylvinyl)triethylsilane (10a)22: Colorless oil, 22 mg, yield 2922, 2849, 1654, 1632, 1492, 1445, 1264, 1073, 896, 816, 761, 746.
1
72%. H NMR (300 MHz, CDCl3) δ 7.33-7.19 (m, 10H), 6.23 (s, 1H),
0.85 (t, J = 7.8, 9H), 0.76 (q, J = 7.8, 6H). 13C NMR (75 MHz, CDCl3) δ
Acknowledgements
158.0, 143.6, 142.8, 129.5, 128.0, 127.7, 127.5, 127.3, 127.2, 126.7,
7.5, 4.4. IR (KBr, cm−1) 3056, 3023, 2952, 2873, 1486, 1457, 1584, We thank the National Natural Science Foundation of China (No.
1334, 1261, 1090, 1014, 819, 719.
21372224, 21420102003, and 21232008), the Ministry of Science
(2-(4-chlorophenyl)-2-phenylvinyl)triethylsilane (10b)： Colorless and Technology of China (973 Program2011CB808600), Shandong
oil, 24 mg, yield 74%. 1H NMR (400 MHz, CDCl3) δ 7.34-7.13 (m, 9H), Province independent innovation and achievements transformation
6.25-6.21 (d, 1H), 0.88-0.83 (m, 9H), 0.41-0.32 (m, 6H). 13C NMR (100 of special (2014XGC06001), and the Chinese Academy of Sciences for
MHz, CDCl3) δ156.8, 156.7, 143.2, 142.3, 142.1, 141.3, 133.4, 133.3, financial support.
130.9, 129.4, 128.5, 128.1(1), 128.1(0), 128.0, 127.9, 127.7, 127.6,
127.5, 127.4, 127.2, 7.5, 4.5, 4.4. HRMS (EI): calculated C20H25SiCl:
328.1414, found: 328.1415. IR (KBr, cm−1) 2952, 2873, 1486, 1457,
Notes and references
1
(a) C. K. Prier, D. A. Rankic and D. W. C. MacMillan, Chem. Rev.
2013, 113, 5322; (b) B. Zhang and A. Studer, Chem. Soc. Rev.
2015, 44, 3505;(c) S. Tang, K. Liu, C. Liu and A. Lei, Chem. Soc.
Rev. 2015, 44, 1070;(d) J.-R. Chen, X.-Y. Yu and W.-J. Xiao,
Synthesis 2015, 45, 604; (e) C. Liu, D. Liu and A. Lei, Acc. Chem.
Res. 2014, 47, 3459;(f) H. Togo, Advanced free radical
reactions for organic synthesis. Elsevier: UK, 2004.
1584, 1334, 1261, 1090, 1014, 819, 719, 700.
4-phenyl-3-(tetrahydrofuran-2-yl)-2H-benzo[g]chromen-2-one
(12b): Pale yellow oil, 50 mg, yield 74%. 1H NMR (500 MHz, CDCl3) δ
8.57 – 8.51 (m, 1H), 7.74 (dd, J = 6.7, 2.4 Hz, 1H), 7.56 (m, 2H), 7.50 –
7.41 (m, 4H), 7.32 – 7.27 (m, 1H), 7.18 – 7.14 (m, 1H), 6.88 (d, J = 8.8
Hz, 1H), 4.67 – 4.58 (m, 1H), 4.04 – 3.97 (m, 1H), 3.74 (m, 1H), 2.35
(m, 1H), 2.16 – 2.06 (m, 1H), 1.95 – 1.88 (m, 1H), 1.82 – 1.75 (m, 1H).
13C NMR (126 MHz, CDCl3) δ 158.4, 152.3, 149.0, 133.6, 133.4, 127.8,
127.7, 127.6(7), 127.6, 127.5, 127.2, 126.5, 126.0, 124.2, 122.6, 122.1,
121.8, 121.6, 114.5, 75.5, 68.6, 29.1, 26.5. HRMS (ESI): calculated
2
(a) N. Fuentes, W.-Q. Kong, L. Fernández-Sánchez, E. Merino
and C. Nevado, J. Am. Chem. Soc. 2015, 137, 964; (b) W.-Q.
Kong, N. Fuentes, A. García-Domínguez, E. Merino and C.
6 | J. Name., 2012, 00, 1-3
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Nevado, Angew. Chem., Int. Ed. 2015, 54, 2487;(c) W.-Q. Kong,
E. Merino and C. Nevado, Angew. Chem., Int. Ed. 2014, 53
9 (a) J. Li, J. Zhang, H. Tan and D.-Z. Wang, Org. Lett., 2015, 17,
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