Copper‐Catalyzed Intramolecular Electrophilic Carbofunctionalization of Allylic Amides
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Eine endo-selektive kupferkatalysierte Oxyarylierung oder Oxyvinylierung von Allylamiden liefert ausschließlich die anti-Isomere von Oxazin-Sechsringen. Vielfältig substituierte Allylamide und Diaryliodonium- sowie Vinyl(aryl)iodoniumtriflate gehen diese Umwandlung ein.Abstract The first Ir‐catalyzed enantioselective allylation of trisubstituted allylic electrophiles has been developed. Through modification of the leaving group of allylic electrophiles, we found that trisubstituted allylic phosphates are suitable electrophiles for asymmetric allylation. The reaction of allylic phosphates with enol silanes derived from dioxinones gave allylated products in good yields with high enantioselectivities.
Substitution reaction
Silanes
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This review highlights recent developments in the area of transition metal-catalyzed allylic substitution reactions with unactivated allylic substrates.
Substitution reaction
Substitution (logic)
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A nickel-catalyzed cross-electrophile coupling of allylic acetates and gem-difluorovinyl tosylate is presented, which first achieves allylic gem-difluoroolefins via C(sp3)–C(sp2) cross-electrophile coupling. In addition, this protocol was performed under mild reaction conditions, affording a variety of allylic gem-difluorovinyl arenes in moderate to good yields. Moreover, both linear and branched allylic acetate could produce a linear cross-coupling product exclusively. Mechanistic studies reveal that the reaction involves two different Ni(0)/Ni(II) catalytic cycles.
Coupling reaction
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Allylic chlorides react with phenylselenosodium (3) or phenyltellurosodium (4) followed by chloramine-T to give allylic toluenesulfonamides [1–2]. Previously [3], we reported the synthesis of optically active allylic toluenesulfonamides from the corresponding allylic - and -pinene chlorides. The reduction of allylic toluenesulfonamides with sodium in liquid ammonia affords allylic amines, which are useful synthetic precursors [4–8]. Comparing the reactivity of seleno- and telluroorganic compounds in a one-step toluenesulfonamidation reaction, we demonstrated that better results can be obtained using the telluroorganic compounds. In contrast to easy isolable allylic phenylselenides, allylic phenyltellurides are very unstable and undergo an air oxidation. The secondary allylic-pinene chloride in the reaction with phenylseleno- or phenyltellurosodium rearranges to give primary allylic phenylselenide or allylic phenyltelluride. Herein, we investigated the possibility of using the reactions of optically active allylic carene chlorides with phenylselenosodium or phenyltellurosodium to the synthesis of the corresponding optically active toluenesulfonamides and amines. (–)-4Chloro-3(10)-carene (1) and (+)-10-chloro-3-carene (2), described in our previous paper [9], were chosen for the study.
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Atom-efficient stoichiometric silylcupration reactions of acetylenes followed by electrophilic trapping of the intermediate vinylcopper species with allylic phosphates have been developed. The reaction sequence was also carried out with the use of a catalytic amount of CuCN employing of both allylic phosphates and allylic phosphinates as electrophiles. The methods developed provide an easy access to silylated 1,4-diene systems.
Stoichiometry
Diene
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While the synthesis of biaryls has advanced rapidly in the past decades, cross-Ullman couplings of aryl chlorides, the most abundant aryl electrophiles, have remained elusive. Reported here is the first general cross-Ullman coupling of aryl chlorides with aryl triflates. The selectivity challenge associated with coupling an inert electrophile with a reactive one is overcome using a multimetallic strategy with the appropriate choice of additive. Studies demonstrate that LiCl is essential for effective cross-coupling by accelerating the reduction of Ni(II) to Ni(0) and counteracting autoinhibition of reduction at Zn(0) by Zn(II) salts. The modified conditions tolerate a variety of functional groups on either coupling partner (42 examples), and examples include a three-step synthesis of flurbiprofen.
Coupling reaction
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In this context, we successfully utilize polycyclic aryl-activated alkyl ammonium triflates as the electrophilic aryl-activated alkylating agent in the nickel-catalyzed hydroxyl- or sulfonamide-directed cross-electrophile coupling reaction with an array of phenyl benzoates, allowing for the synthesis of various aryl ketones under mild conditions.
Sulfonamide
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Allylic alcohols were readily converted into allylic iodides by hydrogen iodide generated in situ from chlorotrimethylsilane/sodium iodide and water, or alcohols, under mild conditions. Displacement of allylic alcohols containing a terminal double bond gave allylic iodides accompanied by allylic rearrangement. This procedure has successfully been extended to a one-pot synthesis of homoallylic alcohols by carrying out successive Barbier type reactions.
Hydrogen iodide
Sodium iodide
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Abstract The allylic selenides (I) react with the compounds (II) to produce the selenilimines (III) which undergo allylic rearrangement, forming the protected primary amines (IV).
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It has been shown that Pd(CH 3 CN) 2 Cl 2 catalyzes the rearrangement of allylic esters. Carbamates rearrange more rapidly than acetates which in turn rearrange more rapidly than carbonates. Allylic carbamates are more rapidly isomerized by Pd(CH 3 CN) 2 Cl 2 than by Hg(OCOCF 3 ) 2 . The rearrangement proceeds well except in cases where the central carbon of the allylic system is fully substituted.In contrast to the reported rearrangement of allylic carbamates by Hg 2+ and previous reports of Pd 2+ -catalyzed rearrangements of allylic esters, this work showed the latter are extremely E specific; thus, E allylic acetates yield equilibrium mixtures free of Z allylic isomers, under conditions in which Z allylic acetates are unreactive. This E specificity is applied to stereospecific 1,3-diene synthesis from bis E,Z-allylic acetates.
Stereospecificity
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