Enantioselective Intramolecular Hydroamination Catalyzed by Lanthanide Ate Complexes Coordinated by N-Substituted (R)-1,1‘-Binaphthyl-2,2‘-diamido Ligands

Abstract

Ytterbium and lutetium ionic complexes derived from enantiopure substituted (R)-binaphthylamine ligands, of the general formula [Li(THF)n][Ln[(R)-C20H12(NR)2]2], have been investigated for the hydroamination/cyclization of several aminopentenes and an aminohexene. Complexes with isopropyl or cyclohexyl substituents on nitrogen atoms were found to be efficient catalysts under mild conditions for the formation of N-containing heterocycles with enantiomeric excesses up to 78%.

Internal Alkene Hydroaminations Catalyzed by Zirconium(IV) Complexes and Asymmetric Alkene Hydroaminations Catalyzed by Yttrium(III) Complexes

“…[8] Addition of 7 to 3 (5 mol %), followed by heating at 100 8C for 105 h, then afforded the pyrrolidine 14 in 97 % yield by NMR. Alternatively, cyclization of 7 at 120 8C (benzene-d 6 ) and 150 8C (toluened 8 ) provided 14 in 94 % (12 h) and 98 % (2.5 h) yield, respectively.…”

“…[9] The use of 5 mol % 32 as a precatalyst afforded 14 in 95 % yield (56 % ee, entry 2). Also, treatment of 7 with 5 mol % 33 in benzene-d 6 (25 8C, 18 h, entry 4) or toluene-d 8 (25 8C, 15 h, entry 5) afforded 14 in 95 % yield (61 % ee). Use of the yttrium catalyst derived from 1,2-diamine ligand (25) gave a racemic mixture (entry 6).…”

Inter‐ and Intramolecular Palladium‐Catalyzed Allyl Cross‐Coupling Reactions Using Allylindium Generated In Situ from Allyl Acetates, Indium, and Indium Trichloride

“…With allyl acetates as coupling partners, the presence of a methyl group at the a, b, or g position had an effect both on reaction rates and on product yields. Allyl acetate (2), but-1-en-3-yl acetate (23), crotyl acetate (24), and 2-methylallyl acetate (25) afforded the corresponding allylic compounds in good yields in cross-coupling reactions. Treatment of 1-iodonaphthalene with allyl acetate gave 1-al- [b] 33 0 6 SMe 16 7 18 [b] 76 0 7 S O 2 Ph 14 10 78 9 0 8 C l 2 0 3 2 1 8 [b] 40 0 80, 8 [c] lylnaphthalene (26) in 81 % yield under the optimized conditions (Table 3, entry 2), while exposure of 1-iodonaphthalene to the allylindium derived from 23 produced the desired products 27 and 28 in 57 % yield, but with the product 27 resulting from a-attack predominating (a/g 3.7:1) ( Table 3, entry 3).…”

“…[23] The results are summarized in Table 4. Treatment of 50 with Pd, In, and InCl 3 in the presence of N,N-dimethyl-n-butylamine and LiCl as an additive gave the desired compound 61 in 86 % yield (Table 4, entry 1).…”

Homogeneous Catalytic Hydroamination of Alkynes and Allenes with Ammonia

“…An even more appealing process would be the addition of NH 3 to carbon-carbon multiple bonds, a process that would occur ideally with 100 % atom economy. [7] Although various homogeneous catalysts, including alkali metals, [8] early [9] and late transition metals, [10] and d- [11] and f-block elements, [12] have been used to effect the so-called hydroamination reaction, none of them were reported to be effective when NH 3 is used as the amine partner. [13] Herein we report that cationic gold(I) complexes supported by a cyclic (alkyl)(amino)carbene (CAAC) [14] ligand readily catalyze the addition of ammonia to a variety of unactivated alkynes and allenes to provide a diverse array of linear and cyclic nitrogen-containing compounds.…”