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Synlett 2010(3): 407-410  
DOI: 10.1055/s-0029-1219196
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Straightforward Approach towards Substituted Morita-Baylis-Hillman Products via Hydrostannation of Acetylenic Ketones

B. Vasantha Lakshmi, Uli Kazmaier*
Institut für Organische Chemie, Universität des Saarlandes, 66123 Saarbrücken, Germany
Fax: +49(681)3022409; e-Mail: u.kazmaier@mx.uni-saarland.de;
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Publikationsverlauf

Received 21 October 2009
Publikationsdatum:
14. Januar 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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18

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.