First author et al.
Report
Synthesis of Bicyclic Privileged Structures or Privileged Substructures.
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Experimental
(1) General Procedure for the Reductive homo-Coupling
In a 20 mL tube, 1 (0.4 mmol, 2 equiv.), Pd(OAc)2 (1 mol%, 0.5
mg) and Cs2CO3 (0.4 mmol, 2.0 equiv.) were added and charged
with argon more than three times (The tube was sealed with tip-
ping plug). Indene (A8, 0.4 mmol, 2 equiv.) and DMF (3 mL) was
injected into the tube via syringes. The mixture was stirred at
room temperature for 15 minutes, and then placed in
a
pre-heated oil bath at 90 °C stirring at 900 rpm for 24 h. After the
reaction was completed, ethyl acetate and water were added and
extracted in a separatory funnel. The extracted organic phase was
combined and dried with Na2SO4. The solvent was removed by
rotary evaporator. The crude product was purified with chroma-
tography column on silica gel.
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Aryl−Aryl Bond Formation One Century after the Discovery of the
Ullmann Reaction. Chem. Rev. 2002, 102, 1359-1470; (b) Alberico, D.;
Scott, M. E.; Lautens, M., Aryl−Aryl Bond Formation by
Transition-Metal-Catalyzed Direct Arylation. Chem. Rev. 2007, 107,
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Palladium-Catalyzed Coupling Reactions of Aryl Electrophiles through
the Use of P(t-Bu)3 and PCy3 as Ligands. Acc. Chem. Res. 2008, 41,
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(2) General Procedure for the Reductive Cross-Coupling
In a 20 mL tube, 1 (0.2 mmol, 1 equiv.), 1’ (0.4 mmol, 2
equiv.), Pd(OAc)2 (2 mol%, 0.9 mg) and Cs2CO3 (0.8 mmol, 4.0
equiv.) were added and charged with argon more than three times
(The tube was sealed with tipping plug). Indene (A8, 0.6 mmol, 3
equiv.) and DMF (3 mL) was injected into the tube via syringes.
The mixture was stirred at room temperature for 15 minutes, and
then placed in a pre-heated oil bath at 90 °C stirring at 900 rpm for
24 h. After the reaction was completed, ethyl acetate and water
were added and extracted in a separatory funnel. The extracted
organic phase was combined and dried with Na2SO4. The solvent
was removed by rotary evaporator. The crude product was purified
with chromatography column on silica gel or preparative TLC
(PTLC).
(3) General Procedure for the Synthesis of 12 and 14-Membered
Rings
zerovalent
nickel.
Coupling
of
aryl
halides
with
In a 100 mL round-bottom flask, 4 (0.2 mmol, 1 equiv.),
Pd(OAc)2 (5 mol%, 2.2 mg) and Cs2CO3 (0.6 mmol, 3.0 equiv.) were
added and charged with argon more than three times (The tube
was sealed with tipping plug). Indene (A8, 0.4 mmol, 2 equiv.) and
DMF (50 mL) was injected into the tube via syringes. The mixture
was stirred at room temperature for 15 minutes, and then placed
in a pre-heated oil bath at 110 °C stirring at 900 rpm for 24 h. After
the reaction was completed, DMF was removed by vacuum distil-
lation. Then, ethyl acetate and water were added and extracted in
a separatory funnel. The extracted organic phase was combined
and dried with Na2SO4. The solvent was removed by rotary evapo-
rator. The crude product was purified with chromatography col-
umn on silica gel or preparative TLC (PTLC).
bis(1,5-cyclooctadiene)nickel(0). J. Am. Chem. Soc. 1971, 93,
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Supporting Information
The supporting information for this article is available on the
Acknowledgement
Financial support was received from the National Natural Sci-
ence Foundation of China (No. NSF22061038, NSF22067018), Long
Yuan Youth Innovative Project of Gansu Province (2019−39) and
the Northwest Normal University Young Scholars Research Capac-
ity Improvement Program (No. NWNU-LKQN-2020-04). Computa-
tions reported in this paper were performed on the computer
clusters at the Centre for Scientific Modeling and Computation,
CUHK.
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Coupling Reactions. Org. Lett. 1999, 1, 1205-1208.
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Powerful Single-Electron Reducing Agents in Organic Synthesis.
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