Regioselective hydrocarbonylation of phenylacetylene to α,β-unsaturated esters and thioesters with Fe(CO)5 and Mo(CO)6

Larvicidal Activity of Cinnamic Acid Derivatives: Investigating Alternative Products for Aedes aegypti L. Control

“…: 33–34 °C (lit. 31.2–32.2 °C, [ 44 ]; TLC (hexane); R f = 0.2; IR ʋmax (KBr, cm −1 ): 3067, 3036, 2945, 1717, 1638, 1578, 1454, 1315, 1171, 772 [ 45 ]; 1 H-NMR (CDCl 3 , 400 MHz): δ H 7.70 (1H; d ; J = 16.0 Hz), 7.53–7.51 (2H; m ), 7.39–7.37 (3H; m ), 6.44 (1H; d ; J = 16.0 Hz), 3.80 (3H; s ); 13 C-NMR (CDCl 3 , 100 MHz): δ C 51.8, 117.9, 128.2, 129.0, 130.4, 134.5, 145.0, 167.5 [ 46 ].…”

“…Ethyl cinnamate ( 3 ): Yellow oil; Yield 84.9% (252.3 mg, 1.43 mmol); TLC (hexane); R f = 0.22; IR ʋmax (KBr, cm −1 ): 3061, 3028, 2982, 1712, 1639, 1578, 1450, 1312, 1177, 768 [ 45 ]; 1 H-NMR (CDCl 3 , 400 MHz): δ H 7.69 (1H; d ; J = 16.0 Hz), 7.53–7.51 (2H; m ), 7.39–7.37 (3H; m ), 6.44 (1H; d ; J = 16.0 Hz), 4.27 (2H; q ; J = 7.2 Hz), 1.34 (3H; t ; J = 7.2 Hz); 13 C-NMR (CDCl 3 , 100 MHz,): δ C 14.1, 60.5, 118.3, 128.2, 129.0, 130.3, 134.6, 144.7, 167.1 [ 44 , 46 , 47 , 48 ].…”

Ligand‐Controlled Regiodivergent Thiocarbonylation of Alkynes toward Linear and Branched α,β‐Unsaturated Thioesters

“…[1] Meanwhile,t he development of catalytic processes for selective transformations is one of the key goals in organic synthesis.B yc ontrolling the regioselectivity,branched and linear products can be obtained selectively from the same substrates.A lthough recent years have witnessed the successes of regioselective hydroformylation, [2] alkoxycarbonylation, [3] and aminocarbonylation, [4] the development of regioselective thiocarbonylation has been much limited. [5][6][7][8][9][10] This might be partly due to the strong binding affinities of sulfur-containing compounds to latetransition metals affecting the coordination of ligand with catalyst. [11] And the selectivity of the catalyst system is mainly influenced by the properties of the ligands.…”

“…[14] Besides classic condensation reactions, [13] the thiocarbonylative transformation of alkynes provides an ideal option for producing a,b-unsaturated thioesters. [6][7][8][9] Thefirst example on transition-metal-catalyzed thioformylation of acetylenes was reported by Ogawa and Sonoda" group in 1990s (Scheme 1A,t op), and as mall amount of the thiocarbonylation products could be observed when palladium catalyst was used. [6b] Their subsequent work showed that platinum catalysts could improve the selectivity toward the branched product (Scheme 1A,bottom).…”

“…[6c,d,f] Them ain contributions of palladium-catalyzed thiocarbonylation were accomplished by Xiao,A lper et al [7] who mainly focused on the transformation of allenes, [7b] vinylcyclopropanes, [7g] 1,3-dienes. [7b,d,e,f] However,t hiocarbonylation reactions of alkynes have been very rarely reported, [8,9] and it is likewise limited by the poor selectivity,m ore unfortunately,t od ate,a lmost no functional groups are compatible within this class of reactions (Scheme 1B). Under this premise,wewondered whether anew catalytic blueprint could be designed to afford high regioselectivity and excellent functional group compatibility for the thiocarbonylation of alkynes.W eb een able to realize this goal finally after extensive systematic studies.Our protocol is characterized by its ligand-controlled regioselectivity pattern, wide substrate scope and unprecedented functional group compatibility (Scheme 1C).…”