Transition metal-catalysed cross-coupling reactions of P-activated enols

Abstract

Transition metal catalysed cross-coupling reactions are ubiquitous in organic chemistry providing an impressive technique for C-C bond formation. Whilst many electrophilic partners have been described for these reactions, aryl and vinyl phosphates, phosphonates and phosphonites can offer advantages in terms of preparation, stability and reactivity profile. This critical review summarises the advances made to date utilising P-activated enols in metal-catalysed cross-coupling reactions (97 references).

Divergent Synthetic Access toE- andZ-Stereodefined All-Carbon-Substituted Olefin Scaffolds: Application to Parallel Synthesis of (E)- and (Z)-Tamoxifens

“…The combined organic phase was washed with water,b rine, dried (Na 2 SO 4 )a nd concentrated. The obtained crude solid was purified by SiO 2 gel column chromatography (hexane/AcOEt 20:1) to give (4E)-13 as yellow crystals (84 mg 17.6, 22.7, 81.8, 113.2, 115.1, 127.2 (2C), 128.3, 128.6, 128.7 (2C), 142.0, 157.4, 158.1 ppm;I R( neat): ñ max = 2962, 2924, 2218, 1580, 1443, 1377, 1323, 1234, 1063 In ap rocedure similar to the preparation of (E)-7,t he reaction of (Z)-5b-1 (204 mg, 1.00 mmol) in CF 3 2, 22.6, 124.6, 126.7 (2C), 127.1, 128.0 (2C), 143.6, 146.4, 175.3 ppm;I R( neat): ñ max = 2999, 2669, 1657, 1506, 1435, 1308, 1279, 1206, 1153 In ap rocedure similar to the preparation of (E)-8,t he reaction of (Z)-5b-1 (1.43 g, 7.0 mmol) with DIBAL (20.6 mL, 21.0 mmol;1 .02 m in toluene) gave (Z)-8 as ac olorless oil (1.11g,9 8% 3335,2918,1599,1491,1441,1242,997,763,700 In ap rocedure similar to the preparation of (E)-8',t he reaction of (Z)-8 (744 mg, 4.59 mmol) using Ac 2 O( 562 mg, 5.51 mmol), DMAP (28 mg, 5mol %), and Et 3 N(557 mg, 5.51 mmol) gave (Z)-8' as acolorless oil (849 mg, 91 %, E/Z = 2:> 98). 1 3, 20.9, 21.2, 66.7, 125.8, 126.6, 127.9 (2C) In aprocedure similar to the preparation of (E)-14 a,t he reaction of (Z)-8' (102 mg, 0.5 mmol) using MeLi (3.37 mL, 3. 3, 17.3, 21.1, 28.3, 125.7, 128.0 ChemistryOpen 2017, 6,73-89 www.chemistryopen.org 2017 The Authors.…”

Cross‐Coupling of Aryl‐Bromide and Porphyrin‐Bromide on an Au(111) Surface

“…[1,2] Cross-coupling reactions allow chemists to design andm anipulate delicate and complex molecules. [3][4][5][6][7][8] These reactions have been proved useful for the synthesis of many important products, such as drugs,m aterials, and optical devices. [9][10][11] Recently,i th as been demonstrated that coupling reactions can take place on solids urfaces, known as on-surface synthesis.…”

Vinyl Nosylates: An Ideal Partner for Palladium‐Catalyzed Cross‐Coupling Reactions

“…The related mesylates, [9,10] tosylates, [10,11] and even phosphates [12] have been explored, although with some drawbacks, mostly due to their introduction mode, but also with some success, especially with tosylates. We reasoned that the leaving-group ability of arylsulfonates in the first step (oxidative addition) of the catalytic cycle could easily be tuned with electron-withdrawing substituents.…”