Application of mixed phosphorus/sulfur ligands based on terpenoids to Pd-catalyzed asymmetric allylic substitution and Rh-catalyzed hydrogenation
Konstantin N. GavrilovIlya V. ChuchelkinVladislav K. GavrilovIlya D. FirsinValeria M. TruninaAlexei A. ShiryaevAlena O. ShkirdovaEvgeniya V. BermeshevaВ. А. ТафеенкоВладимир В. ЧернышевVladislav S. ZimarevNataliya S. Goulioukina
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Abstract:
A small library of easily prepared diamidophosphite-sulfides based on 1,3-thioether alcohols, primarily of terpenoid nature, was developed. Upon complexation with Pd(II) ions, these hemilabile ligands showed the ability to form bothKeywords:
Substitution (logic)
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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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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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Abstract This review describes the different Pd‐catalyzed methods that afford allylic amines from intermolecular reactions between allylic alcohols and amines and, with personal comments, the mechanisms that have been proposed. Allylic amines are an important class of compounds, while a wide structural variety of allylic alcohols are commercially available and are abundant in nature. The advantages of the use of allylic alcohols over that of their derivatives such as allylic esters or carbonates are the high atom efficiency and the formation only of water as the by‐product. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
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The palladium(0)-catalyzed reactions of the primary and secondary allylic sulfoximines 7, 9, 11, 13, 15, 17, and 19 gives allylic sulfinamides without 1,3-allylic rearrangement. These compounds were not isolated but were converted to their corresponding N-tosyl allylic amines, primary and secondary 8, 10, 12, 14, 16, 18, and 20, respectively. In the case of the optically active secondary allylic sulfoximines 17 and 19, chiral N-tosyl allylic secondary amines were formed in high enantiomeric purities.
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The Mislow-Evans rearrangement of α, β-and α, γ-disubstituted allylic sulfoxides (2) to (E)-allylic alcohols (4) was found to occur under acidic conditions. By combination of this method with a catalytic oxidation of allylic sulfides (1), a novel one-pot transformation of allylic sulfides (1) to 4 was achieved.
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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.
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Sodium iodide
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Polyvinylpyrrolidone
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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.
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