A highly efficient three-component coupling reaction between thioformamides and organolithium and Grignard reagents was developed. The generality of the process has been demonstrated by using various combinations of reactants and reagents.
T. Murai, F. Asai, J. Am. Chem. Soc., 2007, 129, 780-781.
A three-component, Ni-catalyzed reductive coupling enables a convergent synthesis of tertiary benzhydryl amines, which are challenging to access by traditional reductive amination methodologies. The condensation of secondary N-trimethylsilyl amines with benzaldehydes provides iminium ions in situ, which react with several distinct classes of organic electrophiles.
C. Heinz, J. P. Lutz, E. M. Simmons, M. M. Miller, W. R. Ewing, A. G. Doyle, J. Am. Chem. Soc., 2018, 140, 2292-2300.
A Lewis acid palladium-catalyzed reaction of amides, aryl aldehydes, and arylboronic acids enables a practical and general synthesis of α-substituted amides from simple, readily available building blocks.
T. Beisel, G. Manolikakes, Org. Lett., 2013, 15, 6046-6049.
Asymmetric arylation of aldimines catalyzed by heterogeneous chiral rhodium nanoparticles proceeded in aqueous media to afford chiral (diarylmethyl)amines in high yields with outstanding enantioselectivities. This heterogeneous catalyst system exhibited very high turnover numbers. The reusability of the catalyst was also demonstrated.
T. Yasukawa, T. Kuremoto, H. Miyamura, S. Kobayashi, Org. Lett., 2016, 18, 2716-2718.
A catalyst prepared in situ from Rh(I) and a chiral diene ligand enables a rapid synthesis of enantiomerically enriched tosyl-protected diarylmethylamines from arylboronic acids and N-tosylaldimines under mild conditions. This addition offers access to diarylmethylamines in good yields with excellent chiral purity at room temperature using MeOH as a solvent and NEt3 as a base.
C.-C. Chen, B. Gopula, J.-F. Syu, J.-H. Pan T.-S. Kuo, P.-Y. Wu, J. P. Henschke, H.-L. Wu, J. Org. Chem., 2014, 79, 8077-8085.
A highly efficient asymmetric arylation of N-nosylimines with arylboronic acids catalyzed by a rhodium-diene complex enables the synthesis of a wide range of enantiopure N-(diarylmethyl)nosylamides, as well as (3S)-2-(4-nosyl)-3-phenylisoindolin-1-one in high yields under very mild conditions.
L. Wang. Z.-Q. Wang, M.-H. Xu, G.-Q. Lin, Synthesis, 2010, 3263-3264.
Monosubstituted C1-symmetric dicyclopentadienes as a new class of diene ligands enable a rhodium-catalyzed asymmetric arylation of N-tosylarylimines in excellent yields with high enantioselectivities. The preparation of these diene ligands relied on an efficient lipase-catalyzed resolution as the key step.
C. Shao, H.-J. Yu, N.-Y. Wu, C.-G. Feng, G.-Q. Lin, Org. Lett., 2010, 12, 3820-3823.
A new type of C2-symmetric chiral diene ligand was applied successfully in the Rh-catalyzed asymmetric arylation of N-tosylarylimines with arylboronic acids to give a broad range of highly enantiomerically enriched diarylmethylamines as well as 3-aryl substituted phthalimidines.
Z.-Q. Wang, C.-G. Feng, M.-H. Xu, G.-Q. Lin, J. Am. Chem. Soc., 2007, 129, 5336-5337.
The use of a new C2-symmetric diene ligand (1R,4R)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene (Ph-bod*) for the rhodium-catalyzed asymmetric arylation of N-tosylarylimines with arylboroxines allowed asymmetric synthesis of diarylmethylamines with high enantioselectivity.
N. Tokunaga, Y. Otomaru, K. Okamoto, K. Ueyama, R. Shintani, T. Hayashi, J. Am. Chem. Soc., 2004, 126, 13584-13585.
P-chiral P,π-hybrid ligands are both sterically and electronically tunable at the substituents on the phosphorus atom and the π-system of the ligand. Catalytic asymmetric addition of boronic acids to imines proceeds with high levels of enantioinduction in the presence of these ligands.
J. D. Sieber, D. Chennamadhavuni, K. R. Fandrick, B. Qu, Z. S. Han, J. Savoie, S. Ma, L. P. Samankumara, N. Grinberg, H. Lee, J. J. Song, C. H. Senanayake, Org. Lett., 2014, 16, 5494-5497.
The asymmetric arylation of N-tosylarylimines with arylboronic acids was realized by using rhodium/(S)-ShiP as catalyst in aqueous toluene to give diarylmethylamines in good yields and enantioselectivities.
H.-F. Duan, Y.-X. Jia, L-X. Wang, Q.-L. Zhou, Org. Lett., 2006, 8, 2567-2569.
The asymmetric synthesis of diarylmethyl amines was realized by rhodium-catalyzed asymmetric addition of aryl titanium reagents to N-alkylidene sulfonamides.
T. Hayashi, M. Kawai, N. Tokunaga, Angew. Chem., 2004, 116, 6251-6252.
Chiral 2-methoxy-1-naphthylsulfinyl-based phenyl backbone sulfoxide-olefin ligands enable highly enantioselective Rh-catalyzed additions of arylboronic acids to N,N-dimethylsulfamoyl-protected aldimines to afford a broad range of chiral diarylmethylamines in high yields with excellent enantioselectivities. Moreover, efficient enantioselective arylation of cyclic N-sulfonylimines was also achieved.
F. Xue, Q. Liu, Y. Zhu, Y. Huang, J. Ge, B. Wan, Synthesis, 2020, 52, 1498-1511.
A chiral bicyclic bridgehead phosphoramidite (briphos) ligand derived from 1-aminoindane was efficient for the Rh-catalyzed enantioselective 1,2-arylation of N-sulfonyl imines, while that derived from 1,2,3,4-tetrahydro-1-naphthylamine was efficient for 1,4-arylation of α,β-unsaturated cyclic ketones. For α,β-unsaturated N-tosyl ketimines, the briphos derived from 1-aminoindane selectively provided γ,γ-diaryl N-tosyl enamines.
A. Lee, H. Kim, J. Org. Chem., 2016, 81, 3520-3527.
A selective rhodium/phosphoramidite-catalyzed synthesis of diarylmethyl amines gave high enantioselectivities and high yields. The small and cheap N,N-dimethylsulfamoyl protecting group was easily removed by a microwave-assisted transamination.
R. B. C. Jagt, P. Y. Toullec, D. Geerdink, J. G. de Vries, B. L. Feringa, A. J. Minnaard, Angew. Chem. Int. Ed., 2006, 45, 2789-2791.