CLUSTER
Silver-Catalyzed Direct Addition of Terminal Alkynes
2761
Table 2 Substrate Scope of the Alkyne–Ketone Addition in Water (continued)
R2
O
HO
R1
AgCl (10 mol%), RuPhos (20 mol%)
R1
R2
+
H
DBU (20 mol%), H2O, 100 °C
1
2
3
Entry
8
Product 3
Yield (%)
79
Entry
16
Product 3
Yield (%)a
56
Ph
OH
HO
HO
3p
Ph
3h
a Isolated yield.
Soc. 2002, 124, 5638. (c) Wei, C.; Mague, J. T.; Li, C.-J.
Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 5749.
Acknowledgment
We are grateful to the Canada Research Chair Foundation (C.J.L.),
the Canada Foundation for Innovation (CFI), NSERC and FQRNT
for support of our research. Z.H.J. acknowledges the Oversea Study
Program of Guangzhou Elite Project for financial support.
(8) (a) Wei, C.; Li, C.-J. J. Am. Chem. Soc. 2003, 125, 9584.
(b) Huang, B.; Yao, X.; Li, C.-J. Adv. Synth. Catal. 2006,
348, 1528. (c) Wei, C. M.; Li, Z. G.; Li, C.-J. Org. Lett.
2003, 5, 4473. (d) For a recent review, see: Yoo, W.-J.;
Zhao, L.; Li, C.-J. Aldrichimica Acta 2011, 44, 43. (e) Wei,
C.; Li, Z.; Li, C.-J. Synlett 2004, 1472. (f) Zani, L.; Bolm, C.
Chem. Commun. 2006, 4263. (g) Peshkov, V. A.;
Pereshivko, O. P.; Van der Eycken, E. V. Chem. Soc. Rev.
2012, 41, 3702.
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(17) General Reaction Procedure: Degassed CH2Cl2 (0.25 mL)
was added to a microwave tube containing the ligand
RuPhos (23.2 mg, 0.05 mmol) and AgCl (3.6 mg, 0.025
mmol) under argon. The resulting suspension was stirred at
r.t. until a clear, colorless solution was obtained; then the
solvent was removed under vacuum. Cyclohexanone (1a; 26
μL, 0.25 mmol), DBU (7.5 μL, 0.05 mmol) and degassed
H2O (0.5 mL) were subsequently added under argon
followed by the addition of phenylacetylene (2a; 104 μL, 1
mmol) using a syringe pump over 12 h. The reaction mixture
was stirred for another 12 h at 100 °C, then cooled and
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© Georg Thieme Verlag Stuttgart · New York
Synlett 2012, 23, 2758–2762