Conjugate Addition of Organocuprates to Diethyl Vinylphosphonate

Baylis−Hillman-Type Carbon−Carbon Bond Formation of Alkenylphosphonates by the Action of Lithium Diisopropylamide

“…Conjugate addition of nucleophiles to alkenylphosphonates bearing a second electron-withdrawing group at the α-position has been established as a rout to alkylphosphonates . Recently, the conjugate addition of organocoppers or enolates to alkenylphosphonates lacking an activating group has been reported . We have been involved in studies directed toward the development of enantioselective conjugate additions of organometallics to activated olefins .…”

α‐Methylene‐β‐amino Ketone Derivatives from β‐Ketoallylsilanes.

“…H NMR (CDCl 3 , 200 S7 MHz) δ -0.04 (s, 9H, Si(CH 3 ) 3 ), 1.09 (t, J = 7.3 Hz, 3H, CH 3 CH 2 C=O), 5H, C=CH(CH 3 ), CH 2 Si), 2.67 (q, J = 7.3 Hz, 2H, CH 3 CH 2 C=O), 6.60 (q, J = 6.6 Hz, 1H, C=CH).13 C NMR (CDCl 3 , 50 MHz) δ -0.9 (Si(CH 3 ) 3 ), 9.2 (CH 3 CH 2 C=O), 15.2 (CH 2 Si), 15.8 (C=CH(CH 3 ),), 30.1 (CH 3 CH 2 C=O), 132.7 (C=CH), 141.1 (C=CH), 202.0 (C=O). GC-MS m/z 184 [M + ] (1This compound was prepared from 282 mg of 4b(1.01 mmol), according to the general procedure described for 2d using the (R)-2,2-dimethyl-[1,3]dioxolane-4-carbaldehyde (195 mg, 1.51 mmol).The crude was purified by chromatography on silica gel (hexane/diethyl ether=9/1) to obtain a mixture of Z/E (114 mg, 0.44 mmol) in the ratio of 10/1 (44% total yield). Spectral data of 2h (Z):IR (CHCl3 ): 1672, 1633 cm -1 .…”

Lewis Acid-Catalyzed Intramolecular [2 + 2] Cycloaddition of α-Ester-Substituted Conjugated Dienyl- and Trienylphosphonates. New Synthesis of Functionalized Cyclic Terpenoids

“…Vinylphosphonates are of synthetic interest due to their usefulness as electrophiles , and because of their biological activities . We have recently reported that vinylphosphonates containing an ene component underwent a Lewis acid-catalyzed intramolecular ene reaction to give phosphono group-containing carbocyclic compounds, which are versatile intermediates for the synthesis of bicyclic compounds and of Cadalane and Valerenic acid sesquiterpenoids .…”