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DOI: 10.1055/s-2008-1042809
Platinum-Catalyzed Tandem Cyclization-Nazarov Cylization Reactions: An Easy Access to Complex Carbocyclic Molecules from 2-Alkenyl-(1′-hydroxyl-4-en-2-ynyl)benzenes
Publication History
Publication Date:
26 February 2008 (online)
Abstract
In the presence of PtCl2/CO catalyst, 2-alkenyl-(1′-hydroxyl-4-en-2-ynyl)benzenes undergo a tandem electrophilic 6-exo-dig cyclization-Nazarov cyclization sequence to give 1H-cyclopenta[a]naphthalenes efficiently and regioselectively.
Key words
alcohols - alkynes - carbenoids - catalysis - tandem reactions
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References and Notes
Magnesium oxide was added to remove Brønsted acid given from PtCl2 and water in this system. We envisage that Brønsted may enhance the transformation of alcohol substrate 13 into indene derivative 24 through a simple Nazarov cyclization as depicted in Scheme [6] .
14See ref. 7d for the formation mechanism of the ketone product 36.
15
Typical Procedure for the Synthesis of 4-Methyl-1-[2-(prop-1-en-2-yl)phenyl]pent-4-en-2-yn-1-ol (3)
To a THF (15 mL) solution of 2-bromobenzaldehyde (1.00 g, 5.40 mmol) was added tributyl(prop-1-en-2-yl)stannane (1.87 g, 1.05 mmol), Pd(PPh3)4 (311 mg, 0.27 mmol), CuCl (0.80 g, 8.10 mmol) and LiBr (0.7 g, 8.10 mmol); the mixture was heated in a sealed tube at 60 °C for 8 h. The resulting solution was concentrated under reduced pressure, and the residues were eluted through a silica column (hexane-EtOAc, 98:2) to afford 2-(prop-1-en-2-yl)benz-aldehyde (639 mg, 4.37 mmol, 81%) as colorless oil. To a THF (8 mL) solution of 2-methylbut-1-en-3-yne (0.29 g, 4.45 mmol) was slowly added n-BuLi (1.6 mL, 2.5 M in hexane) at -78 °C; the solution was stirred for 30 min at -78 °C before addition of a THF solution (2 mL) of 2-(prop-1-en-2-yl)benzaldehyde (0.50 g, 3.42 mmol). After 30 min, to this solution was added H2O (3 mL); the solution was extracted with EtOAc, and concentrated to afford crude alcohol. The crude product was eluted through a silica column (hexane-EtOAc, 5:1) to afford substrate 3 (640 mg, 3.01 mmol, 88%) as a light yellow oil.
Typical Procedure for the 6-
exo
-
dig
-Nazarov tandem cyclization of 4-Methyl-1-(2-prop-1-en-2-yl)phenylpent-4-en-2-yn-1-ol(1) to 1,5-Dimethyl-1
H
-cyclopenta[
a
]naphthalene (4)
A long tube containing PtCl2 (6.3 mg, 0.023 mmol) was evacuated and backfilled with CO. After repeating this procedure twice, the tube was charged with alcohol substrate 3 (100 mg, 0.472 mmol) and dry THF (2 mL). The resulting mixture was stirred at 23 °C for 20 h. The solution was concentrated and eluted through a silica column (hexane) to give compound 4 (81 mg, 0.417 mmol, 89%) as viscous oil.
4-Methyl-1-[2-(prop-1-en-2-yl)phenyl])pent-4-en-2-yn-1-ol (3)
IR (neat): 3654 (m), 1624 (m), 1610 (m) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.76 (d, J = 7.0 Hz, 1 H), 7.33-7.29 (m, 2 H), 7.17 (d, J = 7.0 Hz, 1 H), 5.79 (s, 1 H), 5.32 (s, 1 H), 5.25 (s, 1 H), 5.24 (s, 1 H), 4.99 (s, 1 H), 2.12 (s, 3 H), 1.89 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 144.0, 142.4, 137.5, 128.0, 127.8, 127.4, 127.1, 126.1, 122.1, 116.0, 88.7, 87.1, 61.8, 25.3, 23.1. HRMS: m/z calcd for C15H16O: 212.1201; found: 212.1204.
1,5-Dimethyl-1
H
-cyclopenta[
a
]naphthalene (4)
IR (neat): 1598 (m) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.96 (d, J = 8.0 Hz, 1 H), 7.68 (d, J = 8.0 Hz, 1 H), 7.44 (t, J = 8.0 Hz, 1 H), 7.36 (t, J = 8.0 Hz, 1 H), 7.31 (s, 1 H), 6.53 (s, 1 H), 3.58 (s, 2 H), 2.69 (s, 3 H), 2.22 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 145.6, 142.9, 137.2, 133.0, 129.9, 129.8, 127.6, 125.6, 125.1, 123.7, 123.6, 120.8, 41.5, 19.7, 16.8. HRMS: m/z calcd for C15H14: 194.1096; found: 194.1092.