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DOI: 10.1055/s-0029-1219196
A Straightforward Approach towards Substituted Morita-Baylis-Hillman Products via Hydrostannation of Acetylenic Ketones
Publication History
Publication Date:
14 January 2010 (online)
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Abstract
Regioselective molybdenum-catalyzed hydrostannations of acetylenic ketones give rise to allenoxystannanes, which can be subjected to subsequent aldol reactions. Because aldehydes are not affected under the reaction conditions used, the hydrostannation-aldol addition can be performed as a one-pot reaction, providing easy access to substituted Morita-Baylis-Hillman-type products in a highly stereoselective fashion.
Key words
aldol addition - alkynes - enolates - hydrostannation - molybdenum - Morita-Baylis-Hillman
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References and Notes
General Procedure for One-Pot Hydrostannation-Aldol Additions The acetylenic ketone (1.0 mmol), hydroquinone (10 mol%), and Mo(CO)3 (CNt-Bu)3 (MoBI3) (3 mol%) were dissolved in THF (3 mL) in a Schlenk tube under N2. Then Bu3SnH (1.2 mmol) and the corresponding aldehyde (1.2 mmol) were added, the flask was evacuated and flushed with CO. The mixture was warmed to 60 ˚C for 6 h. After cooling to r.t., the solvent was removed in vacuo, and the reaction mixture was subjected to column chromatography (silica, EtOAc-hexanes).
20
Analytical Data
of Selected ProductsAldol Product 4a
¹H
NMR (400 MHz, CDCl3): δ = 7.73
(dd, J = 8.4,
1.6 Hz, 2 H), 7.50 (tt, J = 7.6,
1.6 Hz, 1 H), 7.40-7.34 (m, 4 H), 7.32-7.26 (m,
2 H), 7.23-7.19 (m, 1 H), 5.91 (td, J = 7.6,
1.2 Hz, 1 H), 5.55 (s, 1 H), 3.24 (br s, 1 H, OH), 1.79 (q, J = 7.6 Hz, 2
H), 1.31 (sext, J = 7.6
Hz, 2 H), 0.75 (t, J = 7.6
Hz, 3 H) ppm. ¹³C NMR (100 MHz, CDCl3): δ = 200.1,
141.5, 141.4, 137.7, 134.7, 133.3, 129.2, 128.4, 128.3, 127.6, 126.3,
76.5, 31.7, 22.2, 13.5 ppm. HRMS (CI): m/z calcd
for C19H20O2 [M]+:
280.1463; found: 280.1461.
Aldol Product
(
Z
)-6a
¹H
NMR (400 MHz, CDCl3): δ = 8.13
(d, J = 8.4
Hz, 2 H), 7.45 (d, J = 8.4
Hz, 2 H), 7.25-7.03 (m, 3 H), 7.06 (dd, J = 8.4,
1.6 Hz, 2 H), 5.92 (t, J = 7.6
Hz, 1 H), 5.42 (s, 1 H), 3.27 (br s, 1 H, OH), 2.90-2.70
(m, 4 H), 2.18 (q, J = 7.6
Hz, 2 H), 1.45 (sext, J = 7.6
Hz, 2 H), 0.91 (t, J = 7.6
Hz, 3 H) ppm. ¹³C NMR (100 MHz, CDCl3): δ = 203.0,
150.6, 147.0, 146.9, 140.6, 140.5, 128.5, 128.3, 126.2, 126.0, 123.5,
69.8, 39.5, 30.8, 30.1, 22.0, 14.0 ppm.
Aldol
Product (
E
)-6a
¹H
NMR (400 MHz, CDCl3): δ = 8.14
(d, J = 8.8
Hz, 2 H), 7.47 (d, J = 8.8
Hz, 2 H), 7.29-7.18 (m, 3 H), 7.11 (dd, J = 8.4,
1.6 Hz, 2 H), 6.87 (t, J = 7.6
Hz, 1 H), 5.69 (s, 1 H), 3.08-2.91 (m, 2 H), 2.85 (t, J = 7.6 Hz,
2 H), 2.43 (sext, J = 7.6
Hz, 1 H), 2.34 (sext, J = 7.6
Hz, 1 H), 1.56 (sext d, J = 7.6,
2.0 Hz, 2 H), 1.00 (t, J = 7.6
Hz, 3 H) ppm. ¹³C NMR (100 MHz, CDCl3): δ = 203.0,
150.6, 147.0, 146.9, 140.6, 140.5, 128.5, 128.3, 126.3, 126.0, 123.5,
69.9, 39.5, 30.8, 30.1, 22.0, 14.0 ppm. HRMS (CI): m/z calcd
for C21H23NO4 [M]+:
353.1627; found: 353.1647.