Photoinduced Metalation of Nonactivated C−Cl Bonds with Samarium Diiodide:  Synthesis of Alkenes with High (Z)-Selectivity through β-Elimination Reactions

Abstract

[reaction: see text] The photoinduced metalation of nonactivated C-Cl bonds of O-acetyl chlorohydrins is promoted by samarium diiodide. As a result of this, beta-elimination of O-acetyl chlorohydrins is achieved, affording the corresponding (Z)-alkenes with total or high stereoselectivity.

A Selective Ru‐Catalyzed Semireduction of Alkynes to Z Olefins under Transfer‐Hydrogenation Conditions

“…( Z )‐3‐Decene [( Z )‐18] :26 Yield: 133 mg (0.95 mmol, 96 %). R f =0.95 (pentane); 1 H NMR (300 MHz, CDCl 3 ): δ= 5.37–5.19 (m, 2 H), 2.04–1.84 (m, 4 H), 1.34–1.12 (m, 8 H), 0.88 (t, J =7.5 Hz, 3 H), 0.81 ppm (t, J =6.8 Hz, 3 H); 13 C NMR (75 MHz, CDCl 3 ): δ= 131.5, 129.4, 31.8, 29.8, 29.0, 27.1, 22.7, 20.6, 14.4, 14.1 ppm; IR (film): $\tilde \nu $ =2959 (m,), 2924 (s), 2855 (m), 1459 (w), 1210 (w), 906 (s), 730 cm −1 (s); MS (EI): m / z (%): 140 (21) [ M ] + , 111 (6), 97 (15), 83 (13), 69 (45), 55 (100).…”

Sustainable Chemistry Metrics

“…For example, in Scheme 6 a chlorine-acetate fragment is lost to give a double bond. [52] If the molecular weight of the starting skeleton is not very high, the reaction would have a low AE.…”

Nickel-Catalyzed Cross-Coupling Reactions of Alkyl Aryl Sulfides and Alkenyl Alkyl Sulfides with Alkyl Grignard Reagents Using (Z)-3,3-Dimethyl-1,2-bis(diphenylphosphino)but-1-ene as Ligand

“…1-Dodecanethiol (0.93 g, 4.6 mmol) was recovered in 92% yield. 19 (Z)-4a, 5b (Z)-5a, 20 (E)-5a, 21 (Z)-5b, 22 (E)-5b, 23 (Z)-5c, 24 (E)-5c, 22 (E)-5d, 25 (Z)-5e, 26 (E)-5e, 27 (E)-5f, 28 7a, 29 and 7b 30 showed the identical spectra reported in the literature. Products 2h and 2p are identical to commercially available reagents.…”