Palladium-Catalyzed Domino Reaction for Stereoselective Synthesis of Multisubstituted Olefins: Construction of Blue Luminogens

Article abstract of DOI:10.1021/acs.joc.8b00150

The first Pd-catalyzed multicomponent reaction of aryl iodides, alkenyl bromides, and strained alkenes has been developed, which allowed us to synthesize a variety of multisubsituted olefins in yields of 45-96% with excellent stereoselectivity. The configuration of the product was controlled by the configuration of the alkenyl bromides. Moreover, this practical methodology employing readily available substrates was found to be tolerant to a wide range of functional groups. Fifty six examples of highly stereoselective tri- or tetrasubstituted olefins have been successfully synthesized via this methodology. Most of the synthesized tetrasubstituted olefins are good aggregation-induced emission (AIE) luminogens.

Full text of DOI:10.1021/acs.joc.8b00150

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Palladium-Catalyzed Domino Reaction for Stereoselective
Synthesis of Multisubstituted Olefins: Building up Blue Luminogens
Tao-Tao Hao, Hao-Ran Liang, Ying-Han Ou-Yang, Chang-Zhen Yin,
Xue-Li Zheng, Mao-Lin Yuan, Rui-Xiang Li, Hai-Yan Fu, and Hua Chen
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00150 • Publication Date (Web): 29 Mar 2018
Downloaded from http://pubs.acs.org on March 29, 2018
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PalladiumꢀCatalyzed Domino Reaction for Stereoselective Synthesis
of Multisubstituted Olefins: Building up Blue Luminogens
TaoꢀTao Hao, HaoꢀRan Liang, YingꢀHan OuꢀYang, ChangꢀZhen Yin, XueꢀLi Zheng, MaoꢀLin
Yuan, RuiꢀXiang Li, HaiꢀYan Fu,* and Hua Chen*
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Key lab of Green Chemistry and Technology, Ministry of Education; College of Chemistry,
Sichuan University, Chengdu 610064, People’s Republic of China.
Fax: (+86)ꢀ28ꢀ8541ꢀ2904; eꢀmail: scufhy@scu.edu.cn; scuhchen@scu.edu.cn.
Abstract: The first Pdꢀcatalyzed multicomponent reaction of aryl iodides, alkenyl bromides,
and strained alkenes have been developed, which allowed us to synthesize a variety of
multisubsituted olefins in yields of 45%ꢀ96% with excellent stereoselectivity. The
configuration of the product was controlled by the configuration of the alkenyl bromides.
Moreover, this practical methodology employing readily available substrates was found to be
tolerant with wide range of functional groups. 56 examples of high stereoselective triꢀ or
tetrasubstituted olefins have been successfully synthesized via this methodology. Most of the
synthesized tetrasubstituted olefins are good aggregationꢀinduced emission (AIE)
luminogens.
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Introduction
Multisubstituted olefins are one of the major classes of chemical building blocks for organic
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synthesis, the significance of multisubstituted olefins is reflected in pharmaceuticals and
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bioactive natural products, as well as the photoresponsive organomaterials, molecular
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devices, and bioꢀimaging. However, the efficient regioꢀ and stereoselective synthesis of
triꢀand tetrasubstituted olefins has presented a formidable challenge for synthetic organic
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chemists for years. Great efforts have been made to develop the methodology for synthesis of
multisubstituted olefins. The most frequently utilized strategies include direct carbometalation
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of alkynes, transitionꢀmetalꢀcatalyzed carbonꢀheteroatom bond cleaving and crossꢀcoupling
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6a
6a
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reactions, carbonylolefination, olefin metathesis, or using directing groups strategy. The
majority of these methods, however, suffer from the one or more of the following limitations
such as limited availability of starting materials, tedious reaction procedure, poor regioꢀ and
/or stereoselectivity. Therefore, the development of more practical and efficient way for
synthesis of multisubstituted olefins with high stereoselectivity is still highly desirable.
Heck reaction has been considered as a useful method for preparation of substituted olefins,
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which usually features costꢀeffectivity and high stereoselectivity. However, the
Pd(0)ꢀcatalyzed intermolecular Heck reaction has seldom been employed for synthesis of
tetrasubstituted olefins because of the low reactivity, possibly due to the steric hindrance
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exerted by the trisubstitued olefin during the carbopalladation process.
The CatellaniꢀHeck
reaction provides a powerful way for the formation of multiple carbonꢀcarbon bonds in a
tandem process by using norbornene as a transient mediator. Yet, in most cases, the
norbornene is extruded from the target molecules at the end of the reaction. A literature survey
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revealed the incorporation of norbornene as an alkyl chain into an extensive пꢀconjugated
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structure could improve its solubility, which made it the potential of being applicable to
solution processing and easy fabrication of largeꢀarea optoelectronic devices. To our surprise,
the norbornene incorporation reactions are scarce in the literature and always confronted with
the limited functional groups. Besides, the scope in terms of the other alkenes has not been
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well explored. Although Lautens and Perumal groups successively realized the synthesis
of norborneneꢀincorporated tetrasubsituted olefins by Pdꢀcatalyzed reactions of aryl halide,
internal alkyne and norbornene, which involve a sequential insertion of norbornene and
internal alkyne into the arylꢀpalladium bond (Scheme1 a, b), these methods were only limited
to synthesize the tetrasubstituted olefins and usually required the tedious multistep synthesis of
the internal alkyne. So far, only one example for synthesis of trisubstituted olefin containing a
norbornyl group was reported by Catellani in 2001, wherein a stoichiometric amount of
dimeric arylnorbornylpalladium chloride complex was used to react with a large excess of
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alkenyl bromide (10.0 equiv). However, the relatively high cost of arylnorbornylpalladium
complex and poor stereoselectivity greatly precluded the practicability of this method. We
herein developed the first Pdꢀcatalyzed domino reaction of aryl iodides, alkenyl bromides and
norbornene to synthesize various triꢀ and tetrasubstituted olefins with more structural diversity.
In addition, the catalytic system could be extended to other strain alkenes. The reaction
features a wide substrate scope, high functional group tolerance, and high stereoselectivity due
to an intramolecular Heck reaction is involved (Scheme1 c). This methodology could enable
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us to synthesize a new kind skeleton for blue AIE luminogens.
Scheme 1. Representative examples for synthesis of norbornylꢀcontaining multisubstituted
olefins via Catellani reaction.
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Results and Discussion
We initiated our studies by reacting 1ꢀiodoꢀ2ꢀmethoxyꢀbenzene (1a, 0.20 mmol) and
norbornene (3a, 0.6 mmol) directly with (E)ꢀ2ꢀbromovinyl benzene (2a, 0.30 mmol) using a
1
3
catalytic amounts of Pd(OAc)
2
(10 mol%) in the presence of methyl isonicotine (50 mol%)
as ligand and K CO (2.0 equiv.) as base in DMAc at 80 °C for 12 h, only trace amount of the
2
3
desired product was detected (Table 1, entry 1). To our delight, the replacement of methyl
isonicotine with triphenylphosphine successfully afforded the coupling product trisubstituted
olefin Zꢀ4a in 25% yield along with 5.6% of E isomer 4aa (Table 1, entry 2). The
1
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configurations of Zꢀ4a and Eꢀ4aa were confirmed by H NMR analysis (see ESI†). By
carefully screening the conditions (see ESI†, Tables S1ꢀS2) we found that the phosphine
ligand was crucial for the reaction, and no desired product was obtained in the absence of
phosphine ligand (Table 1, entry 4). The triꢀ(2ꢀfuryl) phosphine (TFP) proved to be the most
3
efficient ligand. CH CN and Pd(OAc)
2
were the best solvent and palladium source,
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respectively. The amount of K
2 3
CO also significantly influenced the outcome of the reaction.
When 5.0 equiv of K CO was used, the stereoselectivity of the product towards the Zꢀisomer
2
3
was improved remarkably to 92% (Table 1, entry 6). Raising the temperature to 120 °C further
increased the yield and the stereoselectivity to 82% and 93%, respectively (Table 1, entry 8).
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a
Table 1. Optimization of the reaction conditions
Yield (%)
Entry
1
L+ Solvent
T(℃)
Selectivity of 4a (%)
4
a
4aa
Methyl isonicotine
+
DMAc
80
80
trace
25
trace
5.6
ꢀ
81
2
3
4
5
PPh
3
3
+ DMAc
PPh
+ CH CN
3
80
46
ꢀ
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ꢀ
80
ꢀ
ꢀ
80
TFP + CH
TFP + CH
TFP + CH
3
3
3
CN
CN
CN
80
55
62
73
82
12
5
82
92
92
93
b
6
80
b
7
100
120
6
b
8
TFP + CH
3
CN
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a
All reactions were run using 0.2 mmol of 1a, 1.5 equiv. of 2a, 3.0 equiv. of 3a, 2.0 equiv. of
K
2
3
CO , and 10 mol% of Pd(OAc)
2
, 25 mol% of L in 1.5 mL of solvent for 12h; GC yield,
b
using mesitylene as an internal standard. Reaction run at 5.0 equiv. of K CO .
2
3
Having the optimal conditions in hand, the scope of the reaction was investigated. As
shown in Scheme 2, various trisubstituted olefins could be synthesized by this straightforward
and efficient methodology. Both electronꢀrich and deficient aryl iodides were well tolerated,
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leading to expected products in very good yields with excellent Zꢀselectivity (> 92%) (4aꢀ4h).
Notably, the position of substituents influences the reaction greatly. In comparison with
orthoꢀsubstituted iodobenzene, the metaꢀ or paraꢀ substituted counterparts decreased the
yields dramatically to 45ꢀ56% (4iꢀ4m), accompanied by complicated byꢀproducts, which were
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frequently associated with Catellani reaction. Whereas the use of ethyl 2ꢀiodobenzoate gave
no desired product, might be ascribed to the coordination of carbonyl oxygen to the palladium
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center. And then, the scope of Eꢀ2ꢀarylvinyl bromides was investigated. Here, no significant
effect was observed when the substituents were located on the orthoꢀ, metaꢀ or paraꢀposition
of Eꢀ2ꢀarylvinyl bromides, and generally the reactions gave the corresponding products in
good
yields
with
a
high
Z
stereoselectivity
(4nꢀ4v).
When
(E)ꢀ1ꢀbromoꢀ4ꢀ(2ꢀbromovinyl)benzene that has two different bromine atom was investigated,
only 4v the desired product was obtained, without any Catellani arylation product. We also
carried out the reaction using bromophenyl instead of (E)ꢀ1ꢀbromoꢀ4ꢀ(2ꢀbromovinyl)benzene
under the otherwise identical conditions, the Catallani arylation product was neither detected.
This clearly showed that the present optimized condition is not suitable for the Catellani
arylation. It is noteworthy that the heteroaryl rings, such as pyridine and thiophene were all
tolerated and afforded the desired products in moderate to good yields (4wꢀ4y). Interestingly,
when using Zꢀtype alkenyl bromides instead of its E isomer, the trisubstituted olefins was
generated exclusively in Eꢀconfiguration (4y), which indicated that the configuration of the
product could be controlled by the configuration of the alkenyl bromides. It is noteworthy, that
at this point a relatively low reactivity was observed with Zꢀalkenyl bromide, and only 52%
yield of product was produced (4y versus 4x). The low reactivity of Zꢀalkenyl bromides
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possibly resulted from other side reactions. A literature survey revealed that the Zꢀalkenyl
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bromides may react with the strained alkenes in many different ways. Actually, the reaction
products of Zꢀalkenyl bromides turns out to be very complicated under our standard condition.
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Scheme 2. Synthesis of trisubstituted olefins
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a
All reactions were run using 0.5 mmol of 1, 0.75 mmol of 2, 1.5 mmol of 3a, 2.5 mmol of
K
2
3 2 3
CO , and 10 mol% of Pd(OAc) , 25 mol% of TFP in 3.0 mL of CH CN for 12h; isolated
b
yield. (Z)ꢀ2ꢀ(2ꢀbromovinyl)thiophene was used.
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Encouraged by the attained satisfactory results in synthesis of trisubstituted olefins, we
subsequently tried this procedure to synthesize the tetrasubstituted olefins. When 2,
2
ꢀdiphenylꢀ1ꢀbromoethene was coupled with 1ꢀiodoꢀ2ꢀmethoxybenzene and norbornene under
the established conditions, the tetrasubstituted olefin 5a, confirmed by Xꢀray single crystal
analysis (Figure 1, d), was obtained with the yield of 35% yield, and the majority of the
starting materials were recovered. The low yield was presumably due to the large steric
18
hindrance exerted by two phenyl groups in vinyl bromide. We were pleased to find that the
yield could be improved to 72% simply by prolonging the reaction time to 24 h (Scheme 3,
5
a). By prolonging the reaction time, various tetrasubstituted olefins could be easily accessible
in moderate to good yields (Scheme 3). In case of unsymmetrically (E or Z)ꢀ2,
ꢀdiarylꢀ1ꢀbromoethenes, the reaction could provide the Zꢀ or Eꢀtetrasubstituted olefins
2
stereospecifically, depending on the configuration of 2, 2ꢀdiarylꢀ1ꢀbromoethenes. Particularly,
it even could discriminate such a small difference between the two aryl groups in
2
ꢀphenylꢀ2ꢀ(4ꢀchlorophenyl)ꢀ1ꢀbromoꢀ ethene (Scheme 3, 5rꢀ5v). The structure of compounds
5
v was confirmed by Xꢀray analysis (see ESI†, Table S5). In addition, it should be noted that a
significant amount of geminally disubstituted olefin was observed when using
2ꢀarylꢀ1ꢀbromopropene as the coupling reagent (Scheme 3, 5nꢀ5q), the structure of 5n was
confirmed by the Xꢀray single crystal diffraction (see ESI†, Table S4), which resulted from the
β
ꢀH elimination of the alkylpalladium complex, a catalytic active species. This result
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revealed that the process involved a 5ꢀexoꢀHeck cyclization reaction. When the mixture of
1:1 E/Z ratio of 2, 2ꢀdisubstitutedꢀ1ꢀbromoethenes was submitted to the reaction conditions,
the product was obtained as an inseparable E/Z mixture (Scheme 3, 5w and 5x), the E/Z ratio
of ca. 10:1 for 5w and of ca. 5:1 for 5x. By analyzing the outcome of the reaction of the
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ꢀ(2ꢀbromoꢀ1ꢀphenylvinyl)thiophene (E:Z=1:1), we found the E/Z ratios of the olefin were
turn into 8:1 in the recovered starting materials.
a
Scheme 3. Synthesis of tetrasubstituted olefins
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9
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2
3
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0
1
2
3
4
5
6
7
8
9
0
a
All reactions were run using 0.5 mmol of 1, 0.75 mmol of 2 (Eꢀtype configuration), 1.5 mmol
of 3a, 2.5 mmol of K
2
3 2 3
CO , and 10 mol% of Pd(OAc) , 25 mol% of TFP in 3.0 mL of CH CN
b
c
for 24h; isolated yield. Zꢀtype alkenyl bromide was used; the mixture of 2,
2ꢀdisubstitutedꢀ1ꢀbromoethenes (E:Z=1:1) was used.
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We next investigated the efficacy of this reaction process for other norborneneꢀtype
alkenes by reacting with 1a and 2f under the standard conditions. As shown in Scheme 4, the
norbornene with relatively sensitive functional groups, such as ꢀCHO and ꢀCN reacted
smoothly to generate the corresponding annulated products 6a and 6b in an inseparable
mixture of regioisomers in good to excellent yields. The reaction of
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
,4ꢀdihydroꢀ1,4ꢀepoxynaphthalene only yielded the desired product 6c with only 35% of
isolated yield, probably due to the competing side reaction, which led to a significant amount
of byproduct 6c′，but the yield of 6c was remarkably improved to 56% when using Cs CO as
the base. It was important to note that norbornadiene, a less efficient mediator of the Catellani
process, could also undergo the reaction, just upon switching the base from K CO to Cs CO
2
3
2
3
2
3
,
providing 67% yield of 6d together with 11% yield of 6e. The survived double bond in
product 6d could serve as a valuable synthetic handle for further transformations, such as
12a
epoxidation, dihydroxylation, Catellani type reaction, etc. For example, when 6d was
subjected to our established conditions a secondary Catellani reaction occurred to give 6e in
5
2% yield. In case of dicyclopentadiene bearing two different double bonds, the reaction
proceeded exclusively at the more strained double bond, affording a high yield of mixture of
f and 6g with the ratio of 2:1. In addition, the reaction was scalable and a comparable yield
6
was achieved when the reaction was conducted with 1a in 10 mmol scale, demonstrating the
practical utility of the developed methodology. When using cyclopentadiene instead of
dicyclopentadiene in this reaction we also gained the desired product in comparable yield with
that using dicyclopentadiene, which was attributed to rapid dimerization of cyclopentadiene
under the standard conditions (Scheme 5).
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2
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4
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5
5
5
5
5
5
5
5
5
6
a
Scheme 4. The scope of other strained alkenes
0
1
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4
5
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7
8
9
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1
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3
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6
7
8
9
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1
2
3
4
5
6
7
8
9
0
a
All reactions were run using 0.5 mmol of 1a, 0.75 mmol of 2f, 1.5 mmol of 3, 2.5 mmol of
K CO , and 10 mol % of Pd(OAc) , 25 mol % of TFP in 3.0 mL of CH CN for 12 h; isolated
2
3
2
3
b
c
yield. 1.0 mmol of Cs
2
CO
3 2 3
was used instead of K CO . 10 mmol scale reaction.
Scheme 5. Synthesis of 6f and 6g from cyclopentadiene
13, 15
According to the literature
and the above observed results, a plausible mechanism is
proposed in Scheme 6. First, the reaction of aryl iodide with norbornene in the presence of
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Pd(0) and base, produces an fiveꢀmembered palladacycle A, which coordinates with (E)ꢀvinyl
bromide and followed by oxidative addition to generate an arylpalladium species B. The
complexes B then undergoes reductive elimination to afford C, in which the Eꢀconfiguration
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
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3
3
3
3
3
3
3
4
4
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4
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4
4
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4
4
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5
5
5
5
5
5
5
5
5
6
0
1
2
3
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5
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9
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1
2
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5
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8
9
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1
2
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4
5
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8
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1
2
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0
1
2
3
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6
7
8
9
0
19
of double bond is maintained. A subsequent cisꢀinsertion of the double bond into PdꢀC bond
takes place to form a new palladium species D, which undergoes a CꢀC single bond rotation
followed by a cisꢀcoplanar βꢀH elimination, thus giving the final product 5 with Z double bond
configuration opposite to that in the alkenyl bromides. Alternatively, the βꢀH elimination can
also occur on the methyl group of D and E to deliver the geminally disubstituted olefin 5′. The
mechanism discussed above well reveals the origin of the high stereoselectivity of this
reaction.
Scheme 6. Plausible reaction mechanism.
R
R
R
Br
Ar
I
(E)
Pd(0), base
Oxidative addition
Pd(II)
Pd(IV)
Ar
Br
A
R
R
B
5 (Z)
Ar
Reductive elimination
5'
Ar
-H elimination
-H elimination
R
R
R
Pd(II)
Ar
H
single bond roation
Pd(II)
H
Ar
Pd(II)
Ar
E
C
D
Aggregationꢀinduced emission (AIE) is a phenomenon that a luminogens exhibits weak
luminescence in solution but much enhanced emission in the aggregated state. It is reported
14
that the restriction of intramolecular rotation (RIR) is the main cause of the AIE effect.
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5
5
5
5
5
5
5
5
5
6
Realizing that the presence of the norbornyl group in the molecule would restrict the free
intramolecular rotation, we subsequently measured the photoluminescence (PL) behavior of
these tetrasubstituted olefins to evaluate the effect of the norbonyl group on the molecular
photoluminescence properties. Initially, we measured PL spectra of the compound 5d, as well
as the 1,1,2ꢀtriphenylbutꢀ1ꢀene (3E) for comparison. As expected, the compound 5d exhibited
an evident PL signinal than 3E in the thin film (Figure 1, c). Actually, the RIR effect
introduced by the incorporated norbornyl group (Figure 1, e) imparted these multisubstituted
olefin an obvious AIE properties (see ESI†, Figure S7). Take the compound 5a for example, it
0
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1
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6
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8
9
0
emitted faintly in dilute THF (10 ꢁm), but brightly in the THF/H O mixture with 99% water
2
content, with a 250 fold increment in the PL intensity (Figure 1, a, b). The PL enhancement
was possible due to the low solubility of 5a in water and the aggregation with the water
content increase. In addition, 5a also displays a pronounced deepꢀblue fluorescence in solid
state with the maximum of emission at 451 nm, comparing with tetraphenylethene (TPE) at
20
4
45nm, a wellꢀknown splendid blue luminogen. The quantum yield of 5a was 52.5% in solid
20b
state, slightly higher than that of TPE (49.2%). These phenomena clearly showed that the 5a
is well AIEꢀactive. Furthermore, the good solubility of these tetrasubstituted olefins in organic
2 2 3
solvents such as CH Cl , CH CN, THF and toluene, due to incorporate alkyl chains to the
conjugated skeleton, made it the potential of being applicable to solution processing and easy
11
fabrication of largeꢀarea optoelectronic devices.
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2
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4
5
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7
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9
0
1
2
3
4
5
6
7
8
9
0
−5
Figure 1. a) PL spectra of 5a in THF and THF/H
2
O mixtures. Concentration: 10 M;
excitation wavelength: 330 nm. b) Plot of (I/I –1) values versus the compositions of the
0
THF/H
under UV luminescence. c) PL spectra of 3E, 5a, 5d and TPE in the film state. d) ORTEP of
a. e) Comparison of 5d versus 3E in term of RIR (restriction of intramolecular rotation)
2 2 w
O mixtures. Inset: Photos of 5a in THF/H O mixtures (f = 0, 80, and 95%) taken
5
effect.
Conclusions
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5
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5
5
5
5
5
5
5
6
In conclusion, we have developed a palladium catalyzed multicomponent reaction of
aryl iodide, substituted alkenyl bromide and strained alkenes, which assembles the three
substrates in great ordered sequence, and forms three new carbonꢀcarbon bonds in one pot.
The involved 5ꢀexoꢀintramolecular Heck reaction enabled us to synthesize a variety of
multisubstituted olefins with excellent stereoselectivity. Most remarkably, most of the
synthesized tetrasubstituted olefins are AIEꢀactive. Further studies on the application of the
new AIE materials are currently in progress in our laboratory.
0
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9
0
Experimental section
General Information. All solvents, reagents and deuterated solvents were purchased from
Aldrich, Adamas and TCI. Column chromatography was performed with silica gel (Merck,
1
3
00ꢀ400 mesh). H NMR spectra were recorded on Bruker Avance 400 MHz or 600 MHz
spectrometers. Chemical shifts were reported in ppm referenced to 7.26 ppm of chloroformꢀd
2.50 ppm of DMSOꢀd ). The following abbreviations were used to explain multiplicities: s =
(
6
singlet, d = doublet, t = triplet, q = quartet. Coupling constants, J, were reported in Hertz unit
1
3
(
Hz). C NMR spectra were recorded on Bruker Avance 100 MHz or 150 MHz
spectrometers, and were fully decoupled by broad band proton decoupling. Chemical shifts
were reported in ppm referenced to the center line of a triplet at 77.16 ppm of chloroformꢀd
(
39.52 ppm of DMSOꢀd ). HRMS was recorded on a commercial apparatus (ESI Source,
6
TOF). Melting points were obtained by XT4A micro Meltingꢀpoint Measurement Instruments.
Solution state UVꢀVisible spectra were measured by Shimadzu UVꢀ3600 spectrophotometer,
fluorescence spectra were measured using a Edison RFꢀ5301PC spectrofluoremeter. Starting
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materials 2i, 2j, 2k, 2z, 2za were synthesized following literature protocols.
The synthesis of substituted styryl bromide (2bꢀ2h, 2lꢀ2y). Adapted from a previously
21
reported procedure with some modification. α，βꢀUnsaturated carboxylic acid (2.0 mmol)
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
was added to a solution of LiOAc (0.4 mmol) in 10 mL of CH CNꢀH O (97:3 v/v). After the
3
2
mixture was stirred for 5 min at room temperature, Nꢀhalosuccinimide (2.2 mmol) was added
as a solid. The progress of the reaction was monitored by TLC (silica gel, nꢀhexaneꢀethyl
acetate 3:2). Usual workup by flash chromatography (silica gel, petroleum ether) afforded the
haloalkene.
Typical procedure for the synthesis 4aꢀ4x, 6aꢀ6g: A dried 25 mL Schlenk tube equipped
with magnetic stirring bar was charged with 1 (0.5 mmol), 2 (0.75 mmol), 3 (1.5 mmol) and
Pd(OAc)
CH CN (3.0 mL). The tube was sealed well, then the solution was stirred at 120 °C for 12 h.
The reaction mixture was cooled down to room temperature, washed with CH Cl (10 mL),
2 2 3
(11.2 mg, 0.05 mmol), TFP (29.5 mg, 0.125 mmol), K CO (332.5 mg, 2.5 mmol),
3
2
2
filtered and then the solvent was evaporated in vacuum. The crude product was finally
purified by chromatography using petroleum ether/ethyl acetate (50:1) as the eluent to afford
the desired products.
Typical procedure for the synthesis 5aꢀ5x: A dried 25 mL Schlenk tube equipped with
magnetic stirring bar was charged with 1 (0.5 mmol), 2 (0.75 mmol), 3 (1.5 mmol) and
Pd(OAc) (11.2 mg, 0.05 mmol), TFP (29.5 mg, 0.125 mmol), K CO (332.5 mg, 2.5 mmol),
2
2
3
CH
The reaction mixture was cooled down to room temperature, washed with CH
filtered and then the solvent was evaporated in vacuum. The crude product was finally
3
CN (3.0 mL). The tube was sealed well, then the solution was stirred at 120 °C for 24 h.
2
Cl (10 mL),
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6
purified by chromatography using petroleum ether/ethyl acetate (50:1) as the eluent to afford
the desired products.
22
(
E)ꢀ1ꢀ(2ꢀbromovinyl)ꢀ2ꢀmethylbenzene (2b). paleꢀyellow liquid (yield: 215.5 mg, 55%);
0
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3
4
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1
H NMR (400 MHz, CDCl ) δ 7.41 – 7.29 (m, 2H), 7.25 – 7.12 (m, 3H), 6.66(d, J = 13.8 Hz,
3
1H), 2.36 (s, 3H).
23
(
E)ꢀ1ꢀ(2ꢀbromovinyl)ꢀ3ꢀmethoxybenzene (2c). colorless liquid (yield: 284.2 mg, 67%);
1
H NMR (400 MHz, CDCl
3
) δ 7.26 – 7.21 (m, 2H), 7.04 (d, J = 14.0 Hz, 1H), 6.88 – 6.83 (m,
H), 6.61 (d, J = 14.0 Hz, 1H), 3.81 (s, 3H).
E)ꢀ1ꢀ(2ꢀbromovinyl)ꢀ3ꢀchlorobenzene (2d). paleꢀyellow liquid (yield: 99.5 mg, 23%);
2
24
(
1
3
H NMR (400 MHz, CDCl ) δ 7.29 (s, 1H), 7.27 – 7.25 (m, 2H), 7.17 (dd, J = 5.0, 1.1 Hz,
1H), 7.05 (d, J = 14.0 Hz, 1H), 6.81 (d, J = 14.0 Hz, 1H).
23
1
(
E)ꢀ1ꢀ(2ꢀbromovinyl)ꢀ4ꢀmethylbenzene (2e). white solid (yield: 321.5 mg, 82%); H
3
NMR (400 MHz, CDCl ) δ 7.22 – 7.17 (m, 2H), 7.13 (d, J = 8.1 Hz, 2H), 7.07 (d, J = 14.0
Hz, 1H), 6.71 (d, J = 14.0 Hz, 1H), 2.33 (s, 3H).
2
3
1
(
E)ꢀ1ꢀ(2ꢀbromovinyl)ꢀ4ꢀfluorobenzene (2f). colorless liquid (yield: 199.7 mg, 50%); H
NMR (400 MHz, CDCl ) δ 7.17 (dd, J = 8.5, 5.3 Hz, 2H), 6.97 (d, J = 14.0 Hz, 1H), 6.93 (dd,
J = 8.4, 8.4 Hz, 2H), 6.60 (d, J = 14.0 Hz, 1H).
3
23
1
(
E)ꢀ1ꢀ(2ꢀbromovinyl)ꢀ4ꢀchlorobenzene (2g). colorless liquid (yield: 198.6 mg, 46%); H
NMR (400 MHz, CDCl ) δ 7.31 – 7.27 (m, 2H), 7.22 (m, 2H), 7.05 (d, J = 14.0 Hz, 1H), 6.76
3
(d, J = 14.0 Hz, 1H).
23
1
(
E)ꢀ1ꢀbromoꢀ4ꢀ(2ꢀbromovinyl)benzene (2h). white solid (yield: 311.5 mg, 60%); H
NMR (400 MHz, CDCl ) δ 7.49 – 7.41 (m, 2H), 7.16 (m, 2H), 7.04 (d, J = 14.0 Hz, 1H), 6.78
3
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(
d, J = 14.0 Hz, 1H).
2
5
(E)ꢀ2ꢀ(2ꢀbromovinyl)pyridine (2i). Prepared according to a procedure reported by Gelson
1
Perin and coworkers; yellow liquid (yield: 164.7 mg, 45%); H NMR (400 MHz, CDCl3) δ
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
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1
2
3
4
5
6
7
8
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3
4
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7
8
9
0
8.54 (d, J = 4.7 Hz, 1H), 7.65 (td, J = 7.7, 1.8 Hz, 1H), 7.39 (d, J = 13.7 Hz, 1H), 7.21 – 7.16
(m, 2H), 7.14 (d, J = 13.7 Hz, 1H).
2
6
(E)ꢀ2ꢀ(2ꢀbromovinyl)thiophene (2j). Prepared according to a procedure reported by
1
Jianbo Wang and coworkers; yellow liquid (yield: 255.5 mg, 68%); H NMR (400 MHz,
CDCl3) δ 7.22 – 7.17 (m, 1H), 7.19 (d, J = 14.0 Hz, 1H), 7.00 – 6.95 (m, 2H), 6.62 (d, J =
1
4.0 Hz, 1H).
2
7
(Z)ꢀ2ꢀ(2ꢀbromovinyl)thiophene (2k). Prepared according to a procedure reported by
1
Anthony Hayford and coworkers; yellow liquid (yield: 139.2 mg, 37%); H NMR (400 MHz,
CDCl3) δ 7.40 (d, J = 5.2 Hz, 1H), 7.34 – 7.31 (m, 2H), 7.07 (dd, J = 5.1, 3.6 Hz, 1H), 6.33
(d, J = 8.0 Hz, 1H).
28
1
(2ꢀbromoetheneꢀ1,1ꢀdiyl)dibenzene (2l). colorless liquid (yield: 464.4 mg, 90%); H
NMR (400 MHz, DMSO) δ 7.43 (m, 3H), 7.36 – 7.28 (m, 3H), 7.27 – 7.17 (m, 5H).
2
9
3,3'ꢀ(2ꢀbromoetheneꢀ1,1ꢀdiyl)bis(methylbenzene) (2m). colorless liquid (yield: 400.5
1
mg, 70%); H NMR (400 MHz, DMSO) δ 7.31 (dd, J = 9.7, 5.9 Hz, 1H), 7.19 (t, J = 7.6 Hz,
2
2
H), 7.12 (d, J = 7.6 Hz, 1H), 7.10 (s, 1H), 7.06 (s, 1H), 7.04 – 6.96 (m, 3H), 2.31 (s, 3H),
13
.25 (s, 3H); C NMR (101 MHz, DMSO) δ 146.4, 139.9, 139.0, 137.7, 137.6, 129.5, 128.9,
128.6, 128.4, 128.3, 127.8, 126.3, 124.6, 106.2, 21.02 , 21.01.
29
3,3'ꢀ(2ꢀbromoetheneꢀ1,1ꢀdiyl)bis(methoxybenzene) (2n). colorless liquid (yield: 413.4
1
3
mg, 65%); H NMR (400 MHz, CDCl ) δ 7.35 – 7.31(m, 1H), 7.22 (t, J = 8.0 Hz, 1H), 6.96 –
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.81 (m, 5H), 6.79 (s, 1H), 6.78 – 6.74 (m, 1H), 3.82 (s, 3H), 3.77 (s, 3H); C NMR (101
MHz, CDCl ) δ 159.3, 159.2, 146.4, 141.7, 140.0, 129.2, 129.1, 121.8, 119.9, 114.9, 113.4,
13.3, 113.2, 105.3, 55.1.
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3,3'ꢀ(2ꢀbromoetheneꢀ1,1ꢀdiyl)bis(chlorobenzene) (2o). paleꢀyellow liquid (yield: 378.2
1
mg, 58%); H NMR (400 MHz, CDCl
3
) δ 7.45 – 7.39 (m, 2H), 7.36 – 7.27 (m, 3H), 7.25 –
1
3
7
1
3
.20 (m, 2H), 7.13 – 7.09 (m, 1H), 6.87 (s, 1H); C NMR (101 MHz, CDCl ) δ 144.6, 141.9,
40.2, 134.7, 134.5, 130.0, 129.9, 129.7, 128.6, 128.0, 127.7, 125.9, 107.6; HRMS (ESI) m/z:
+
Calcd for C14
H
9
BrCl
2
[M+H] : 326.9337; found: 326.9332.
3
,3'ꢀ(2ꢀbromoetheneꢀ1,1ꢀdiyl)bis(bromobenzene) (2p). white solid (yield: 601.5 mg, 72%);
o
1
mp 58 – 60 C; H NMR (400 MHz, CDCl
3
) δ 7.67 – 7.47 (m, 3H), 7.47 – 7.27 (m, 4H),
) δ 144.4, 142.2, 140.4,
32.5, 131.5, 130.5, 130.2, 130.1, 128.4, 126.3, 122.8, 122.6; HRMS (ESI) m/z: calcd for
13
7.20 (d, J = 7.8 Hz, 1H), 6.92 (s, 1H); C NMR (101 MHz, CDCl
3
1
+
C
14
H
9
Br
3
[M+H] : 416.8312; found: 416.8305.
30
4
,4'ꢀ(2ꢀbromoetheneꢀ1,1ꢀdiyl)bis(methylbenzene) (2q). white solid. (yield: 469.5 mg,
o
1
8
4
1
3
2%); mp 47 – 49 C; H NMR (400 MHz, CDCl ) δ 7.23 – 7.20 (m, 4H), 7.13 – 7.10 (m,
1
3
H), 6.70 (s, 1H), 2.40 (s, 3H), 2.34 (s, 3H); C NMR (101 MHz, CDCl
3
) δ 146.8, 138.3,
38.2, 137.9, 136.4, 129.7, 129.2, 129.0, 127.7, 104.1, 21.5, 21.3.
3
1
4
,4'ꢀ(2ꢀbromoetheneꢀ1,1ꢀdiyl)bis(fluorobenzene) (2r). colorless liquid (yield: 400.6 mg,
1
6
8%); H NMR (400 MHz, CDCl ) δ 7.28 (dd, J = 8.8, 5.4 Hz, 2H), 7.17 (dd, J = 8.9, 5.3 Hz,
3
13
2H), 7.10 (t, J = 8.8 Hz, 2H), 6.99 (t, J = 8.7 Hz, 2H), 6.71 (s, 1H); C NMR (101 MHz,
CDCl ) δ 162.8 (d, J = 248.5 Hz), 162.5 (d, J = 247.9 Hz), 145.0, 136.9 (d, J = 3.3 Hz), 134.9
(d, J = 3.4 Hz), 131.7, 131.6, 129.5, 129.4, 115.6 (d, J = 21.6 Hz), 115.5(d, J = 21.6 Hz),
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4,4'ꢀ(2ꢀbromoetheneꢀ1,1ꢀdiyl)bis(bromobenzene) (2s). white solid (yield: 580.2 mg,
32
o
1
3
0%); mp 108 – 110 C； H NMR (400 MHz, CDCl ) δ 7.57 – 7.50 (m, 2H), 7.46 – 7.38 (m,
1
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7
8
9
0
13
2H), 7.22 – 7.14 (m, 2H), 7.09 – 7.02 (m, 2H), 6.79 (s, 1H); C NMR (101 MHz, CDCl ) δ
3
144.9, 139.3, 137.5, 131.9, 131.8, 131.5, 129.3, 122.7, 122.6, 106.3.
21
1
(
E)ꢀ(1ꢀbromopropꢀ1ꢀenꢀ2ꢀyl)benzene (2t). colorless liquid (yield: 294.3 mg, 75%); H
NMR (400 MHz, CDCl ) δ 7.42 – 7.32 (m, 5H), 6.48 (dd, J = 2.3, 1.2 Hz, 1H), 2.27 (dd, J =
3
13
2.5, 1.4 Hz, 3H); C NMR (101 MHz, CDCl
3
) δ 142.0, 141.5, 129.1, 128.4, 126.5, 105.9,
20.2.
(E)ꢀ1ꢀ(1ꢀbromopropꢀ1ꢀenꢀ2ꢀyl)ꢀ3ꢀchlorobenzene (2u). colorless liquid (yield: 262.5 mg,
1
57%); H NMR (400 MHz, CDCl
3
) δ 7.23 (m, 1H), 7.19 – 7.10 (m, 3H), 6.39 (dd, J = 2.5,
13
1.2 Hz, 1H), 2.11 (d, J = 1.3 Hz, 3H); C NMR (101 MHz, CDCl
3
) δ 142.8, 140.5, 134.6,
+
129.9, 127.9, 126.3, 124.3, 106.8, 19.7; HRMS (ESI) m/z: calcd for C
9
H
8
BrCl [M+H] :
230.9571; found: 230.9567.
33
(
E)ꢀ1ꢀ(1ꢀbromopropꢀ1ꢀenꢀ2ꢀyl)ꢀ4ꢀchlorobenzene (2v). colorless liquid (yield: 276.5 mg,
1
60%); H NMR (400 MHz, CDCl
3
) δ 7.20 (m, 4H), 6.37 (d, J = 1.3 Hz, 1H), 2.12 (d, J = 1.3
1
3
Hz, 3H); C NMR (101 MHz, CDCl3) δ 140.5, 139.4, 133.8, 129.2, 128.8, 128.5, 127.3,
06.1, 19.7.
E)ꢀ2ꢀ(1ꢀbromopropꢀ1ꢀenꢀ2ꢀyl)naphthalene (2w). white solid (yield: 393.6 mg, 80%);
1
33
(
o
1
mp 50 – 53 C; H NMR (400 MHz, CDCl
3
) δ 7.86 – 7.78 (m, 4H), 7.52 – 7.46 (m, 3H), 6.61
13
(dd, J = 2.4, 1.2 Hz, 1H), 2.34 (d, J = 1.3 Hz, 3H); C NMR (101 MHz, CDCl3) δ 141.5,
138.3, 133.5, 133.0, 128.3, 127.7, 126.6, 126.4, 125.0, 124.2, 106.1, 19.8.
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E)ꢀ1ꢀ(2ꢀbromoꢀ1ꢀphenylvinyl)ꢀ4ꢀchlorobenzene (2x). colorless liquid (yield: 263.2 mg,
1
45%); H NMR (400 MHz, CDCl
3
) δ 7.44 – 7.25 (m, 3H), 7.21 – 7.16 (m, 4H), 7.12 – 7.03
13
(
m, 2H), 6.69 (s, 1H); C NMR (101 MHz, CDCl
3
) δ 144.9, 138.3, 137.8, 133.3, 130.3,
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128.7, 128.0, 127.8, 127.7, 127.5, 127.4, 126.8, 104.8.
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(
Z)ꢀ1ꢀ(2ꢀbromoꢀ1ꢀphenylvinyl)ꢀ4ꢀchlorobenzene (2y). white solid (yield: 438.7 mg,
o
1
7
5%); mp 78 – 80 C; H NMR (400 MHz, CDCl
.9 Hz, 3H), 7.20 – 7.17 (m, 2H), 7.11 (dd, J = 6.6, 3.2 Hz, 2H), 6.70 (s, 1H); C NMR (101
) δ 146.4, 140.9, 138.0, 134.5, 131.7, 129.1, 128.9, 128.2, 106.2.
ꢀ(2ꢀbromoꢀ1ꢀphenylvinyl)thiophene (2z). Prepared according to a procedure reported by
3
) δ 7.33 – 7.27 (m, 2H), 7.23 (dd, J = 5.1,
13
1
MHz, CDCl
3
2
2
7
Jianbo Wang and coworkers, the mixture of (E:Z=1:1); yellow liquid (yield: 337.9 mg,
1
63%); H NMR (400 MHz, CDCl
3
) δ 7.47 – 7.40 (m, 4H), 7.38 – 7.33 (m, 7H), 7.24 (dd, J =
5
.1, 1.2 Hz, 1H), 7.13 (dd, J = 3.7, 1.2 Hz, 1H), 7.05 (dd, J = 5.1, 3.7 Hz, 1H), 6.93 (dd, J =
13
5.1, 3.7 Hz, 1H), 6.87 (s, 1H), 6.73 (dd, J = 3.6, 1.1 Hz, 1H), 6.49 (s, 1H); C NMR (101
MHz, CDCl3) δ 143.9, 141.4, 140.8, 140.4, 140.2, 138.6, 130.4, 129.4, 128.7, 128.5, 128.5,
1
28.4 ,128.3, 128.1, 128.5, 127.5, 127.2, 126.6, 126.5, 125.6, 104.3; HRMS (ESI) m/z: calcd
+
for C12
H
10BrS [M+H] : 264.9681; found: 264.9685.
2
ꢀ(2ꢀbromoꢀ1ꢀ(4ꢀfluorophenyl)vinyl)thiophene (2za). Prepared according to a procedure
2
7
reported by Jianbo Wang and coworkers, the mixture of (E:Z=1:1); yellow liquid (yield:
1
3
38.2 mg, 60%); H NMR (400 MHz, CDCl ) δ 7.44 (dd, J = 5.1, 1.2 Hz, 1H), 7.36 – 7.29 (m,
3
4H), 7.25 (d, J = 1.2 Hz, 1H), 7.15 – 7.11 (m, 3H), 7.08 – 7.03 (m, 3H), 6.95 (dd, J = 5.1, 3.7
13
Hz, 1H), 6.87 (s, 1H), 6.74 (dd, J = 3.6, 1.1 Hz, 1H), 6.46 (s, 1H); C NMR (101 MHz,
3
CDCl ) δ 162.9 (d, J = 248.1 Hz), 162.7 (d, J = 247.8 Hz), 143.8, 140.3, 139.9, 139.2, 137.5,
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37.4 (d, J = 3.3 Hz), 134.4, 134.3 (d, J = 3.5 Hz), 131.4, 131.3, 130.5, 130.4, 127.6, 127.4,
126.6, 125.9, 115.5 (d, J = 21.6 Hz), 115.5 (d, J = 21.6 Hz), 104.6, 104.2; HRMS (ESI) m/z:
+
calcd for C12
H
9
BrFS [M+H] : 282.9587; found: 282.9583.
1
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(4aR, 9aS, Z)ꢀ9ꢀbenzylideneꢀ5ꢀmethoxyꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethanofluorꢀ
o
1
ene (4a). white solid (yield:123.2 mg, 81%); mp 108 –110 C; H NMR (400 MHz, CDCl
3
) δ
7
1
2
1
1
.42 – 7.27 (m, 5H), 6.91 (t, J = 7.9 Hz, 1H), 6.77 (d, J = 7.9 Hz, 1H), 6.67 (d, J = 8.0 Hz,
H), 6.63 (s, 1H), 3.85 (s, 3H), 3.12 (d, J = 7.1 Hz, 1H), 2.93 (d, J = 7.0 Hz, 1H), 2.55 (s, 1H),
.34 (s, 1H), 1.70 – 1.59 (m, 2H), 1.48 – 1.41 (m, 2H), 1.21 (d, J = 10.0 Hz, 1H), 1.03 (d, J =
13
0.0 Hz, 1H); C NMR (101 MHz, CDCl ) δ 156.4, 144.8, 144.6, 144.2, 143.7, 138.0, 136.8,
3
29.1, 128.3, 127.4, 127.0, 126.6, 117.0, 109.0, 55.2, 51.8, 49.5, 41.8, 40.5, 32.6, 29.3, 28.6;
+
HRMS (ESI) m/z: calcd for C22
H
22O [M+H] : 303.1743; found: 303.1748.
(4aR, 9aS, Z)ꢀ9ꢀbenzylideneꢀ5ꢀmethylꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethanofluorene
13
1
(4b). yellow oil (yield:118.6 mg, 83%); H NMR (400 MHz, CDCl
3
) δ 7.37 (dd, J = 6.8,
3
6
1
1
.1 Hz, 4H), 7.30 – 7.26 (m, 1H), 6.98 (dd, J = 12.7, 7.6 Hz, 2H), 6.82 (t, J = 7.6 Hz, 1H),
.60 (d, J = 1.9 Hz, 1H), 3.03 (d, J = 7.2 Hz, 1H), 2.95 (d, J = 7.1 Hz, 1H), 2.42 – 2.39 (m,
H), 2.37 (d, J = 3.9 Hz, 1H), 2.34 (s, 3H), 1.66 (dd, J = 3.2, 1.9 Hz, 1H), 1.49 – 1.44 (m,
13
H), 1.27 (s, 2H), 1.05 – 1.01 (m, 1H), 0.87 (dd, J = 7.2, 3.9 Hz, 1H); C NMR (101 MHz,
CDCl3) δ 149.0, 147.8, 141.3, 138.9, 134.6, 129.6, 128.7, 128.5, 126.7, 126.3, 122.8, 121.3,
+
53.7, 50.9, 45.4, 40.5, 32.5, 29.9, 28.4, 18.9; HRMS (ESI) m/z: calcd for C H [M+H] :
2
2
22
287.1794; found: 287.1788.
(4aR, 9aS, E)ꢀ9ꢀbenzylideneꢀ5ꢀmethylꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethanofluorꢀ
13 1
3
ene (4bb ). H NMR (400 MHz, CDCl ) δ 7.56 (d, J = 7.6 Hz, 2H), 7.41– 7.36 (m, 3H),
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.22 (t, J = 7.4 Hz, 1H), 7.15 (t, J = 7.5 Hz, 1H), 7.05 (d, J = 7.3 Hz, 1H), 6.90 (d, J = 2.2 Hz,
1H), 3.38 (d, J = 6.8 Hz, 1H), 3.21 (d, J = 6.8 Hz, 1H), 2.46 (d, J = 4.0 Hz, 2H), 2.38 (s, 3H),
.65 – 1.60 (m, 1H), 1.48 (dd, J = 8.0, 1.9 Hz, 2H), 1.27 (s, 1H), 1.06 (d, J = 10.2 Hz, 1H),
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6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
13
0.94 – 0.90 (m, 1H); C NMR (101 MHz, CDCl ) δ 147.6, 146.6, 144.4, 137.8, 134.7, 129.7,
3
128.8, 128.6 , 127.3, 126.3, 119.2, 117.1, 52.8, 51.1, 40.9, 40.3, 32.9, 29.2, 28.9, 18.8.
(4aR, 9aS, Z)ꢀ9ꢀbenzylideneꢀ5,6ꢀdimethylꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethanofluꢀ
1
orene (4c). yellow oil (yield: 117.1 mg, 78%); H NMR (400 MHz, CDCl
3
) δ 7.41 – 7.27 (m,
5
2
2
H), 6.95 (d, J = 8.0 Hz, 1H), 6.75 (d, J = 8.0 Hz, 1H), 6.55 (s, 1H), 3.06 (d, J = 7.2 Hz, 1H),
.96 (d, J = 7.1 Hz, 1H), 2.39 (s, 2H), 2.26 (s, 3H), 2.24 (s, 3H) 1.68 (dd, J = 13.6, 7.0 Hz,
13
H), 1.46 (dd, J = 24.5, 6.0 Hz, 2H), 1.27 (d, J = 10.1 Hz, 1H), 1.04 (d, J = 10.0 Hz, 1H); C
) δ 149.3, 147.9, 139.1, 137.2, 132.9, 128.8, 128.5, 128.2, 126.6,
21.8, 120.9, 53.9, 51.2, 45.4, 41.0, 32.4, 29.9, 28.4, 19.9, 15.9; HRMS (ESI) m/z: calcd for
NMR (101 MHz, CDCl
3
1
+
C
23
H24 [M+H] : 301.1951; found: 301.1949.
(4aR, 9aS, Z)ꢀ9ꢀbenzylideneꢀ5ꢀchloroꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethanofluorene
o
1
(4d). white solid (yield: 126.9 mg, 83%); mp 61– 63 C; H NMR (400 MHz, CDCl
3
) δ 7.39
–
6
1
7.28 (m, 5H), 7.11 (d, J = 7.8 Hz, 1H), 7.02 – 6.98 (m, 1H), 6.84 (dd, J =7.8, 1.6 Hz, 1H),
.66 (s, 1H), 3.13 (d, J = 7.0 Hz, 1H), 2.96 (d, J = 7.1 Hz, 1H), 2.67 (s, 1H), 2.37 (s, 1H),
.73 – 1.60 (m, 2H), 1.53 – 1.37 (m, 2H), 1.21 (d, J = 10.1 Hz, 1H), 1.06 (d, J = 10.1 Hz, 1H);
C NMR (101 MHz, CDCl3) δ 147.6, 147.2, 143.6, 138.4, 131.6, 128.7, 128.6, 128.5, 127.7,
1
3
127.1, 124.4, 122.0, 53.3, 51.4, 45.7, 40.1, 32.5, 29.7, 28.4; HRMS (ESI) m/z: calcd for
+
C
21
H
19Cl [M+H] : 307.1248; found: 307.1250.
(7aS, 11aR, Z)ꢀ7ꢀbenzylideneꢀ7a,8,9,10,11,11aꢀhexahydroꢀ7Hꢀ8,11ꢀmethanobenzo[c]fluoꢀ
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1
rene (4e). white solid (yield: 140.3 mg ,87%); mp 75 – 77 C; H NMR (400 MHz, CDCl
3
) δ
7.98 (d, J = 8.3 Hz, 1H), 7.75 (d, J = 7.9 Hz, 1H), 7.48 (dd, J = 8.2, 1.3 Hz, 1H), 7.44 – 7.35
m, 6H), 7.31 – 7.22 (m, 2H), 6.66 (d, J = 1.2 Hz, 1H), 3.47 (d, J = 7.0 Hz, 1H), 3.09 (d, J =
(
1
1
1
1
1
1
1
1
1
1
2
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2
2
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2
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2
2
2
3
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3
4
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4
4
4
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5
5
5
5
5
5
5
6
0
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2
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6
7
8
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2
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9
0
6.9 Hz, 1H), 2.63 (d, J = 3.5 Hz, 1H), 2.40 (d, J = 1.8 Hz, 1H), 1.78 – 1.59 (m, 3H), 1.50 –
13
1
1
1
.43 (m, 1H), 1.27 – 1.22 (m, 1H), 1.13 – 0.98 (m, 1H); C NMR (101 MHz, CDCl
3
) δ 148.2,
46.9, 138.9, 138.8, 133.9, 130.6, 128.9, 128.6, 128.5, 126.9, 126.8, 126.1, 125.9, 125.0,
22.3, 122.1, 54.2, 50.8, 45.1, 41.3, 32.7, 30.1, 28.5; HRMS (ESI) m/z: calcd for C25H
22
+
[
(
(
M+H] : 323.1794; found: 323.1789.
4aR, 9aS, Z)ꢀ9ꢀbenzylideneꢀ5ꢀfluoroꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethanofluorene
1
4f). yellow oil (yield:117.8 mg, 81%); H NMR (400 MHz, CDCl
3
) δ 7.38 – 7.28 (m, 5H),
6.89 – 6.78 (m, 3H), 6.65 (s, 1H), 3.19 (d, J = 7.2 Hz, 1H), 2.96 (d, J = 7.2 Hz, 1H), 2.49 (s,
H), 2.34 (d, J = 2.8 Hz, 1H), 1.65 (t, J = 2.9 Hz, 1H), 1.47 (d, J = 9.3 Hz, 1H), 1.39 (s, 1H),
1
1
3
1.26 (s, 1H), 1.21 – 1.17 (m, 1H), 1.09 – 1.05 (m, 1H); C NMR (101 MHz, CDCl3) δ 159.9
(
d, J = 245.9 Hz), 146.9 (d, J = 2.2 Hz), 144.6 (d, J = 6.0 Hz), 138.4, 136.4 (d, J = 17.8 Hz),
1
5
2
28.7，128.6, 128.0 (d, J = 7.1 Hz), 127.0, 124.2, 119.5 (d, J = 3.5 Hz), 114.6 (d, J = 20.3 Hz),
+
3.9, 48.5, 45.6, 40.7, 32.6, 29.6, 28.5; HRMS (ESI) m/z: calcd for C21
91.1544; found: 291.1542.
H
19F [M+H] :
(
4aR, 9aS, Z)ꢀ9ꢀbenzylideneꢀ5ꢀ(trifluoromethyl)ꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethꢀ
1
anofluorene (4g). yellow oil (yield:151.5 mg, 89%); H NMR (400 MHz, CDCl ) δ 7.41 –
3
7.26 (m, 7H), 6.98 (t, J = 7.8 Hz, 1H), 6.70 (s, 1H), 3.33 (d, J = 7.1 Hz, 1H), 3.00 (d, J = 7.3
Hz, 1H), 2.52 (s, 1H), 2.38 (s, 1H), 1.71 – 1.59 (m, 2H), 1.53 – 1.35 (m, 2H), 1.27 – 1.22 (m,
13
3
1H), 1.11 – 1.01 (m, 1H); C NMR (101 MHz, CDCl ) δ 147.8, 146.1, 143.5, 138.4, 128.8,
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28.5, 127.4 (q, J = 31.5 Hz), 127.2, 126.9, 126.5, 126.0 (q, J = 5.1 Hz), 124.8 (q, J = 273.6
19 3
Hz), 124.4, 53.8, 50.9, 45.7, 42.6, 32.4, 30.2, 28.2; HRMS (ESI) m/z: calcd for C22H F
+
[
M+H] : 341.1512; found: 341.1517.
0
1
2
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5
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7
8
9
0
1
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(4aR, 9aS, Z)ꢀ9ꢀbenzylideneꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethanofluorene (4h).
1
yellow liquid (yield: 92.2 mg, 67%); H NMR (400 MHz, CDCl
3
) δ 7.39 – 7.26 (m, 5H),
7
1
3
1
1
.23 (dd, J = 7.2, 0.8 Hz, 1H), 7.17 – 7.14 (m, 2H), 6.93 – 6.86 (m, 1H), 6.62 (d, J = 1.8 Hz,
H), 3.07 (d, J = 7.2 Hz, 1H), 2.93 (d, J = 7.1 Hz, 1H), 2.33 (d, J = 3.3 Hz, 1H), 2.30 (d, J =
.3 Hz, 1H), 1.67 – 1.63 (m, 1H), 1.48 – 1.39 (m, 2H), 1.26 (s, 2H), 1.16 (dd, J = 5.9, 4.2 Hz,
13
H), 1.04 – 1.00 (m, 1H); C NMR (101 MHz, CDCl ) δ 150.9, 147.5, 141.4, 138.8, 128.7,
3
28.6, 126.8, 126.1, 125.3, 123.7, 123.0, 53.6, 51.8, 45.6, 42.9, 32.4, 29.6, 28.7; HRMS (ESI)
+
m/z: calcd for C21
H
20 [M+H] : 273.1638; found: 273.1633.
(4aR, 9aS, Z)ꢀ9ꢀbenzylideneꢀ6ꢀmethoxyꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethanofluoꢀ
o
1
rene (4i). white solid (yield: 67.7 mg, 45%); mp 135 – 138 C; H NMR (400 MHz, CDCl
3
) δ
7
1
2
1
.53 (d, J = 7.6 Hz, 2H), 7.46 (d, J = 8.3 Hz, 1H), 7.37 (t, J = 7.7 Hz, 2H), 7.20 (d, J = 7.4 Hz,
H), 6.83 – 6.72 (m, 3H), 3.84 (s, 3H), 3.35 (d, J = 6.7 Hz, 1H), 3.19 (d, J = 6.8 Hz, 1H),
.44 (d, J = 3.7 Hz, 1H), 2.36 (d, J = 3.9 Hz, 1H), 1.58 (d, J = 7.1 Hz, 1H), 1.47 (dd, J = 8.2,
13
.6 Hz, 2H), 1.27 (s, 1H), 1.04 (d, J = 10.2 Hz, 1H), 0.93 (d, J = 10.2 Hz, 1H); C NMR (101
) δ 160.6, 150.1, 146.8, 138.0, 137.3, 128.6, 128.5, 125.9, 120.5, 117.3, 114.0,
09.2, 55.5, 53.5, 51.4, 43.0, 40.4, 32.8, 29.1, 28.9; HRMS (ESI) m/z: calcd for C H O
MHz, CDCl
3
1
2
2
22
+
[M+H] : 303.1743; found: 303.1736.
4aR, 9aS, Z)ꢀ9ꢀbenzylideneꢀ6ꢀmethylꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethanofluorꢀ
(
o
1
3
ene (4j). white solid (yield: 73.8 mg, 52%); mp 105 – 107 C. H NMR (400 MHz, CDCl ) δ
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.56 (d, J = 7.7 Hz, 2H), 7.45 (d, J = 7.9 Hz, 1H), 7.38 (t, J = 7.7 Hz, 2H), 7.21 (t, J = 7.4 Hz,
1H), 7.10 – 7.02 (m, 2H), 6.87 (d, J = 2.1 Hz, 1H), 3.35 (d, J = 6.7 Hz, 1H), 3.19 (d, J = 6.8
Hz, 1H), 2.45 (d, J = 3.7 Hz, 1H), 2.38 (s, 3H), 2.35 (d, J = 4.0 Hz, 1H), 1.67 – 1.61 (m, 2H),
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6
7
8
9
0
13
1.51 – 1.44 (m, 2H), 1.03 (d, J = 10.2 Hz, 1H), 0.97 – 0.91 (m, 1H); C NMR (101 MHz,
CDCl
3
) δ 148.6, 147.2, 141.8, 138.5, 137.9, 128.7, 128.6, 128.1, 126.2, 125.6, 119.4, 118.4,
+
5
3.3, 51.2, 43.1, 40.4, 32.8, 29.1, 28.9, 21.7; HRMS (ESI) m/z: calcd for C22
87.1794; found: 287.1786.
H
22 [M+H] :
2
(4aR, 9aS, Z)ꢀ9ꢀbenzylideneꢀ7ꢀfluoroꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethanofluꢀ
o
1
orene (4k). white solid (yield: 81.2 mg, 56%); mp 77 – 80 C. H NMR (400 MHz, CDCl ) δ
3
7.42 – 7.28 (m, 5H), 7.15 (dd, J = 8.3, 5.5 Hz, 1H), 6.85 (d, J = 8.5, 1H), 6.77 (dd, J = 10.5,
2.4 Hz, 1H), 6.66 (s, 1H), 3.03 (d, J = 7.1 Hz, 1H), 2.96 (d, J = 7.2 Hz, 1H), 2.33 (d, J = 3.1
Hz, 1H), 2.26 (d, J = 3.3 Hz, 1H), 1.65 (s, 2H), 1.48 – 1.36 (m, 2H), 1.18 – 1.15 (m, 1H),
13
3
1.06 – 1.00 (m, 1H); C NMR (101 MHz, CDCl ) δ 161.5 (d, J = 241.8 Hz), 146.7 (d, J = 3.3
Hz), 146.3 (d, J = 2.1 Hz), 143.1 (d, J = 8.6 Hz), 138.1, 128.7, 128.6, 127.2, 125.9 (d, J = 9.0
Hz), 124.3, 115.7 (d, J = 23.3 Hz), 110.1 (d, J = 23.4 Hz), 54.1, 51.1, 45.6, 42.8, 32.3, 29.4,
+
2
8.7; HRMS (ESI) m/z: calcd for C21
H
19F [M+H] : 291.1544; found: 291.1542.
(4aR, 9aS, Z)ꢀ9ꢀbenzylideneꢀ7ꢀmethylꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethanofluorꢀ
1
ene (4l). yellow oil (yield: 78.7 mg, 55%)；H NMR (400 MHz, CDCl
3
) δ 7.45 – 7.36 (m, 4H),
7
.34 – 7.28 (m, 1H), 7.15 (d, J = 8.1 Hz, 1H), 7.02 (d, J = 5.5 Hz, 2H), 6.63 (d, J = 1.5 Hz,
1H), 3.05 (d, J = 7.1 Hz, 1H), 2.95 (d, J = 7.1 Hz, 1H), 2.35 (d, J = 3.3 Hz, 1H), 2.30 (d, J =
.1 Hz, 1H), 2.13 (s, 3H), 1.71 – 1.60 (m, 2H), 1.50 – 1.37 (m, 2H), 1.23 – 1.18 (m, 1H), 1.05
3
1
3
3
– 0.99 (m, 1H); C NMR (101 MHz, CDCl ) δ 148.1, 147.5, 141.5, 138.8, 135.4, 129.7,
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28.8, 128.4, 126.8, 124.9, 124.2, 122.8, 53.9, 51.4, 45.5, 42.8, 32.3, 29.5, 28.7, 21.5; HRMS
+
(ESI) m/z: calcd for C22
H
22 [M+H] : 287.1794; found: 287.1785.
(4aR, 9aS, Z)ꢀ9ꢀbenzylideneꢀ6ꢀfluoroꢀ7ꢀmethylꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethanꢀ
0
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0
1
ofluorene (4m). yellow oil (yield: 73.3 mg, 48%); H NMR (400 MHz, CDCl ) δ 7.39 – 7.27
3
(m, 5H), 6.94 (d, J = 7.6 Hz, 1H), 6.84 (d, J = 9.6 Hz, 1H), 6.55 (d, J = 1.4 Hz, 1H), 3.01 (d,
J = 7.1 Hz, 1H), 2.94 (s, 1H), 2.32 (d, J = 3.1 Hz, 1H), 2.25 (d, J = 3.3 Hz, 1H), 2.01 (d, J =
2
1
.0 Hz, 3H), 1.67 – 1.56 (m, 2H), 1.45 – 1.34 (m, 2H), 1.19 – 1.14 (m, 1H), 1.05 – 1.00 (m,
13
H); C NMR (101 MHz, CDCl3) δ 161.8 (d, J = 247.2 Hz), 150.7 (d, J = 7.6 Hz), 146.5 (d,
J = 1.0 Hz), 138.7, 137.1 (d, J = 2.9 Hz), 128.7, 128.5, 126.8, 126.1 (d, J = 5.5 Hz), 122.6 (d,
J = 18.4 Hz), 121.9 (d, J = 2.5 Hz), 111.2 (d, J = 22.2 Hz), 54.1, 51.5 (d, J = 1.9 Hz), 45.5,
+
42.7, 32.3, 29.4, 28.6, 14.9 (d, J = 3.7 Hz); HRMS (ESI) m/z: calcd for C22
05.1700; found: 305.1691.
(4aR, 9aS, Z)ꢀ5ꢀmethoxyꢀ9ꢀ(2ꢀmethylbenzylidene)ꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmethꢀ
H
21F [M+H] :
3
o
1
anofluorene (4n). white solid (yield: 113.4 mg, 72%); mp 80 – 82 C; H NMR (400 MHz,
CDCl ) δ 7.29 – 7.19 (m, 4H), 6.86 (t, J = 7.9 Hz, 1H), 6.64 (d, J = 8.0 Hz, 1H), 6.55 (s, 1H),
.36 (d, J = 7.8 Hz, 1H), 3.83 (s, 3H), 3.12 (d, J = 7.1 Hz, 1H), 2.96 (d, J = 7.1 Hz, 1H), 2.54
s, 1H), 2.36 (s, 1H), 2.26 (s, 3H), 1.67 – 1.57 (m, 2H), 1.51 – 1.37 (m, 2H), 1.20 (d, J = 10.0
3
6
(
1
3
Hz, 1H), 1.06 – 1.00 (m, 1H); C NMR (101 MHz, CDCl
3
) δ 156.5, 147.8, 143.5, 138.1,
137.9, 136.4, 130.0, 129.1, 127.8, 127.0, 125.9, 122.2, 116.1, 109.5, 55.2, 53.3, 49.5, 45.6,
+
40.0, 32.6, 29.8, 28.6, 20.0; HRMS (ESI) m/z: calcd for C23
H
24O [M+H] : 317.1900; found:
3
17.1891.
(4aR, 9aS, Z)ꢀ5ꢀmethoxyꢀ9ꢀ(3ꢀmethoxybenzylidene)ꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1,4ꢀmeꢀ
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o
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thanofluorene (4o). white solid (yield: 126.2 mg, 76%); mp 159 – 161 C; H NMR (400
MHz, CDCl ) δ 7.51 (d, J = 8.8 Hz, 1H), 7.13 – 6.44 (m, 6H), 6.43 (d, J = 1.6 Hz, 1H), 3.83
s, 3H), 3.75 (s, 3H), 3.11 (d, J = 7.0 Hz, 1H), 2.96 (d, J = 7.0 Hz, 1H), 2.53 (s, 1H), 2.39 (s,
3
(
1
1
1
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2
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2
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3
3
3
4
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4
4
4
5
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5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
3
1H), 1.67 – 1.58 (m, 2H), 1.46 –1.45 (m, 2H), 1.19 (s, 1H), 1.02 (dd, J = 6.3, 5.0 Hz, 1H); C
NMR (101 MHz, CDCl
3
) δ 158.8, 156.6, 148.8, 142.7, 139.7, 138.5, 133.3, 127.8, 122.1,
1
16.3, 115.7, 115.1, 114.6, 109.8, 55.6, 55.3, 53.4, 49.5, 45.3, 39.9, 32.7, 29.7, 28.5; HRMS
+
(
ESI) m/z: calcd for C23
H
24
O
2
[M+H] : 333.1849; found: 333.1841.
(
4aR, 9aS, Z)ꢀ9ꢀ(3ꢀchlorobenzylidene)ꢀ5ꢀmethoxyꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1, 4ꢀmethꢀ
o
1
anofluorene (4p). white solid (yield:121.4 mg, 72%); mp 144 – 145 C; H NMR (400 MHz,
CDCl ) δ 7.28 –7.25 (m, 4H), 6.92 (t, J = 7.9 Hz, 1H), 6.68 (dd, J = 13.6, 7.9 Hz, 2H), 6.51
(d, J = 0.8 Hz, 1H), 3.83 (s, 3H), 3.09 (d, J = 7.1 Hz, 1H), 2.89 (d, J = 7.0 Hz, 1H), 2.52 (d, J
2.6 Hz, 1H), 2.29 (d, J = 2.8 Hz, 1H), 1.67 – 1.56 (m, 2H), 1.50 – 1.33 (m, 2H), 1.15 (d, J =
3
=
13
10.1 Hz, 1H), 1.04 – 0.96 (m, 1H); C NMR (101 MHz, CDCl
3
) δ 156.6, 149.1, 142.6, 140.7,
1
3
3
38.6, 134.2, 129.7, 128.9, 127.7, 127.1, 126.8, 121.4, 116.2, 109.9, 55.3, 53.7, 49.4, 45.5,
+
9.9, 32.5, 29.7, 28.5; HRMS (ESI) m/z: calcd for C22
37.1349.
H21ClO [M+H] : 337.1354; found:
(
4aR, 9aS, Z)ꢀ9ꢀ(3ꢀfluorobenzylidene)ꢀ5ꢀmethoxyꢀ2,3,4,4a,9,9aꢀhexahydroꢀ1Hꢀ1, 4ꢀmethꢀ
o
1
anofluorene (4q). white solid (yield:102.5 mg, 64%); mp 111 – 114 C; H NMR (400 MHz,
CDCl ) δ 7.31 (d, J = 6.1 Hz, 1H), 7.03 – 6.95 (m, 4H), 6.73 – 6.68 (m, 2H), 6.54 (s, 1H),
3
3.84 (s, 3H), 3.09 (d, J = 7.1 Hz, 1H), 2.90 (d, J = 7.1 Hz, 1H), 2.52 (d, J = 2.6 Hz, 1H), 2.30
(
d, J = 2.9 Hz, 1H), 1.63 (d, J = 2.5 Hz, 2H), 1.45 – 1.41 (m, 2H), 1.20 – 1.12 (m, 1H), 1.01
13
3
(dd, J = 6.4, 5.0 Hz, 1H); C NMR (101 MHz, CDCl ) δ 163.0 (d, J = 245.6 Hz), 156.6,
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