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DOI: 10.1055/s-2005-863718
Rhodium-Catalyzed Addition-Cyclization Reactions of 5-Yn-1-ones with Arylboronic Acids
Publication History
Publication Date:
22 February 2005 (online)
Abstract
5-Yn-1-ones react with arylboronic acids in the presence of a catalytic amount of rhodium(I) complex having a diolefin ligand to afford 2-alkylidenecyclopentanols through the regioselective addition of an arylrhodium(I) species across the carbon-carbon triple bond, followed by intramolecular nucleophilic addition of the resulting vinylrhodium(I) species to the carbonyl group.
Key words
rhodium - addition-cyclization reaction - nucleophilic addition - arylboronic acid - 5-yn-1-one
- For reviews on Rh-catalyzed carbon-carbon bond forming reactions, see:
-
1a
Fagnou K.Lautens M. Chem. Rev. 2003, 103: 169 -
1b
Hayashi T.Yamasaki K. Chem. Rev. 2003, 103: 2829 -
2a
Sakai M.Ueda M.Miyaura N. Angew. Chem. Int. Ed. 1998, 37: 3279 -
2b
Batey RA.Thadani AN.Smil DV. Org. Lett. 1999, 1: 1683 -
2c
Fürstner A.Krause H. Adv. Synth. Catal. 2001, 343: 343 -
2d
Moreau C.Hague C.Weller AS.Frost CG. Tetrahedron Lett. 2001, 42: 6957 -
3a
Takezawa A.Yamaguchi K.Ohmura T.Yamamoto Y.Miyaura N. Synlett 2002, 1733 -
3b
Matsuda T.Makino M.Murakami M. Org. Lett. 2004, 6: 1257 -
4a
Miura T.Shimada M.Murakami M. J. Am. Chem. Soc. 2005, 127: 1094 -
4b See also:
Miura T.Sasaki T.Nakazawa H.Murakami M. J. Am. Chem. Soc. 2005, 127: 1390 - For a related transformation of 5-yn-1-als by a nickel catalyst, see:
-
5a
Ni Y.Amarasinghe KKD.Montgomery J. Org. Lett. 2002, 4: 1743 -
5b
Mahandru GM.Liu G.Montgomery J. J. Am. Chem. Soc. 2004, 126: 3698 ; and references cited therein - 6 A report on a similar reaction appeared on the Web during the preparation of this manuscript:
Shintani R.Okamoto K.Otomaru Y.Ueyama K.Hayashi T. J. Am. Chem. Soc. 2005, 127: 54
References
General Procedure for Cyclization of 5-Yn-1-ones.
To an oven-dried, N2-purged flask was added [Rh(OH)(cod)]2 (2.28 mg, 0.5 µmol, 0.05 equiv of Rh), arylboronic acid (1.0 mmol, 5.0 equiv), 1,4-dioxane (1 mL), and H2O (20 µL). A solution of substrate (0.2 mmol, 1.0 equiv) in 1,4-dioxane (1.0 mL) was added to the reaction mixture at r.t. After complete consumption of substrate, H2O was added. The aqueous layer was extracted with EtOAc three times. The combined extracts were washed with brine and dried over MgSO4. The solvent was removed under reduced pressure and the residue was purified by preparative thin-layer chromatography (hexane-EtOAc) to give the product.
When rhodium(I) complex generated in situ from [Rh(OH)(cod)]2 and (R)-BINAP was used, the ee was lower (55% ee) than that of the isolated [Rh(OH)(binap)]2.