| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1344987 | Tetrahedron: Asymmetry | 2015 | 10 Pages |
sTitanium mediated asymmetric Mannich reactions using imidazolidin-2-thione as a chiral auxiliary proceeded in good yields and with high diastereoselectivity to afford the anti-products in the presence of PPh3 additive. A non-chelated transition state with the PPh3-bound titanium enolate was proposed to explain the stereochemistry of the product. Alcoholysis of the adducts with methanol cleaved the imidazolidin-2-thione auxiliary to give the methyl esters in good yields and with excellent ee values.
Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slide
(S)-5-Isopropyl-3-phenyl-2-thioxoimidazolidin-4-oneC12H14N2OS[α]D20 = −53.9 (c 1.00, CHCl3)Absolute configuration: (S)Source of chirality: l-valine
(S)-5-Methyl-3-phenyl-2-thioxoimidazolidin-4-oneC10H10N2OS[α]D20 = −22.8 (c 1.00, CH2Cl2)Absolute configuration: (S)Source of chirality: l-alanine
(S)-5-Benzyl-3-phenyl-2-thioxoimidazolidin-4-oneC16H14N2OS[α]D20 = −245.8 (c 0.16, CH2Cl2)Absolute configuration: (S)Source of chirality: l-phenylalanine
(S)-5-((S)-sec-Butyl)-3-phenyl-2-thioxoimidazolidin-4-oneC13H16N2OS[α]D20 = −47.0 (c 0.14, CH2Cl2)Absolute configuration: (5S,1′S)Source of chirality: l-isoleucine
(S)-5-(tert-Butyl)-3-phenyl-2-thioxoimidazolidin-4-oneC13H16N2OS[α]D20 = −390.5 (c 0.14, CH2Cl2)Absolute configuration: (S)Source of chirality: l-tertiary leucine
(S)-4-Isopropyl-1-phenylimidazolidin-2-thioneC12H16N2S[α]D20 = −36.1 (c 1.00, CH2Cl2)Absolute configuration: (S)Source of chirality: 3-phenyl-2-thioxoimidazolidin-4-one
(S)-4-Methyl-1-phenylimidazolidin-2-thioneC10H12N2S[α]D20 = −183.9 (c 0.16, CH2Cl2)Absolute configuration: (S)Source of chirality: 3-phenyl-2-thioxoimidazolidin-4-one
(S)-4-Benzyl-1-phenylimidazolidin-2-thioneC16H16N2S[α]D20 = −127.6 (c 0.24, CH2Cl2)Absolute configuration: (S)Source of chirality: 3-phenyl-2-thioxoimidazolidin-4-one
(S)-4-((S)-sec-Butyl)-1-phenylimidazolidin-2-thioneC13H18N2S[α]D20 = −70.8 (c 0.16, CH2Cl2)Absolute configuration: (4S,1′S)Source of chirality: 3-phenyl-2-thioxoimidazolidin-4-one
(S)-4-(tert-Butyl)-1-phenylimidazolidin-2-thioneC13H18N2S[α]D20 = −189.4 (c 0.15, CH2Cl2)Absolute configuration: (S)Source of chirality: 3-phenyl-2-thioxoimidazolidin-4-one
(S)-N-Propionyl-4-isopropyl-1-phenylimidazolidin-2-thioneC15H20N2OS[α]D20 = +98.9 (c 1.00, CHCl3)Absolute configuration: (S)Source of chirality: 1-phenylimidazolidin-2-thione
(S)-N-Butyryl-4-isopropyl-1-phenylimidazolidin-2-thioneC16H22N2OS[α]D20 = +79.4 (c 0.17, CH2Cl2)Absolute configuration: (S)Source of chirality: 1-phenylimidazolidin-2-thione
(S)-N-Valeryl-4-isopropyl-1-phenylimidazolidin-2-thioneC17H24N2OS[α]D20 = +92.2 (c 0.15, CH2Cl2)Absolute configuration: (S)Source of chirality: 1-phenylimidazolidin-2-thione
(S)-N-Isovaleryl-4-isopropyl-1-phenylimidazolidin-2-thioneC17H24N2OS[α]D20 = +57.9 (c 0.19, CH2Cl2)Absolute configuration: (S)Source of chirality: 1-phenylimidazolidin-2-thione
(S)-N-Hexanoyl-4-isopropyl-1-phenylimidazolidin-2-thioneC18H26N2OS[α]D20 = +54.6 (c 0.20, CH2Cl2)Absolute configuration: (S)Source of chirality: 1-phenylimidazolidin-2-thione
(S)-N-tert-Butylacetyl-4-isopropyl-1-phenylimidazolidin-2-thioneC18H26N2OS[α]D20 = +92.6 (c 0.17, CH2Cl2)Absolute configuration: (S)Source of chirality: 1-phenylimidazolidin-2-thione
(S)-N-Phenylacetyl-4-isopropyl-1-phenylimidazolidin-2-thioneC20H22N2OS[α]D20 = +107.7 (c 0.22, CH2Cl2)Absolute configuration: (S)Source of chirality: 1-phenylimidazolidin-2-thione
(S)-N-(3-Phenylpropionyl)-4-isopropyl-1-phenylimidazolidin-2-thioneC21H24N2OS[α]D20 = +87.5 (c 0.14, CH2Cl2)Absolute configuration: (S)Source of chirality: 1-phenylimidazolidin-2-thione
(S)-N-Propionyl-4-methyl-1-phenylimidazolidin-2-thioneC13H16N2OS[α]D20 = +225.7 (c 0.11, CH2Cl2)Absolute configuration: (S)Source of chirality: 1-phenylimidazolidin-2-thione
(S)-N-Propionyl-4-benzyl-1-phenylimidazolidin-2-thioneC19H20N2OS[α]D20 = +93.9 (c 0.43, CH2Cl2)Absolute configuration: (S)Source of chirality: 1-phenylimidazolidin-2-thione
(S)-N-Propionyl-4-((S)-sec-butyl)-1-phenylimidazolidin-2-thioneC16H22N2OS[α]D20 = +91.3 (c 0.65, CH2Cl2)Absolute configuration: (4S,1′S)Source of chirality: 1-phenylimidazolidin-2-thione
(S)-N-Propionyl-4-(tert-butyl)-1-phenylimidazolidin-2-thioneC16H22N2OS[α]D20 = +45.2 (c 0.56, CH2Cl2)Absolute configuration: (S)Source of chirality: 1-phenylimidazolidin-2-thione
(5S,2′R,3′S)-5-Isopropyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-phenyl-propionyl]imidazolidin-2-thioneC29H33N3O2S[α]D20 = +123.5 (c 0.28, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Isopropyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-(p-chloro-phenyl)-propionyl]imidazolidin-2-thioneC29H32ClN3O2S[α]D20 = +95.2 (c 0.14, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Isopropyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-(m-nitro-phenyl)-propionyl]imidazolidin-2-thioneC29H32N4O4S[α]D20 = +155.1 (c 0.13, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Isopropyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-(2″,3″-dimethoxyphenyl)-propionyl]imidazolidin-2-thioneC31H37N3O4S[α]D20 = +85.1 (c 0.58, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Isopropyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-(2″-furyl)-propionyl]imidazolidin-2-thioneC27H31N3O3S[α]D20 = +148.3 (c 0.15, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Isopropyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-(2″-thienyl)-propionyl]imidazolidin-2-thioneC27H31N3O2S2[α]D20 = +133.3 (c 0.40, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Isopropyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-phenyl-butyryl]imidazolidin-2-thioneC30H35N3O2S[α]D20 = +165.2 (c 0.11, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Isopropyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-phenyl-valeryl]imidazolidin-2-thioneC31H37N3O2S[α]D20 = +123.6 (c 0.24, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Isopropyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-phenyl-isovaleryl]imidazolidin-2-thioneC31H37N3O2S[α]D20 = +196.7 (c 0.21, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Isopropyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-phenyl-hexanoyl]imidazolidin-2-thioneC32H39N3O2S[α]D20 = +157.1 (c 0.13, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Isopropyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-phenyl-phenylacetyl]imidazolidin-2-thioneC34H35N3O2S[α]D20 = +138.3 (c 0.15, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Isopropyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-phenyl-(3-phenylpropionyl)]imidazolidin-2-thioneC35H37N3O2S[α]D20 = +112.1 (c 0.35, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Methyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-phenyl-propionyl]imidazolidin-2-thioneC27H29N3O2S[α]D20 = +136.2 (c 0.41, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-Benzyl-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-phenyl-propionyl]imidazolidin-2-thioneC33H33N3O2S[α]D20 = +143.8 (c 0.50, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-((S)-sec-Butyl)-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-phenyl-propionyl]imidazolidin-2-thioneC30H35N3O2S[α]D20 = +140.1 (c 0.47, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(5S,2′R,3′S)-5-(tert-Butyl)-3-phenyl-1-[2′-methyl-3′-(p-methoxyphenylamino)-3′-phenyl-propionyl]imidazolidin-2-thioneC30H35N3O2S[α]D20 = +148.7 (c 0.52, CH2Cl2)Absolute configuration: (5S,2′R,3′S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(2R,3S)-Methyl 2-methyl-3-(p-methoxyphenylamino)-3-phenylpropanoateC18H21NO3[α]D20 = −51.1 (c 1.05, CH2Cl2)Absolute configuration: (2R,3S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(2R,3S)-Methyl 2-methyl-3-(p-methoxyphenylamino)-3-(p-chloro-phenyl)propanoateC18H20ClNO3[α]D20 = −42.9 (c 0.55, CH2Cl2)Absolute configuration: (2R,3S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(2R,3S)-Methyl 2-methyl-3-(p-methoxyphenylamino)-3-(m-nitro-phenyl)propanoateC18H20N2O5[α]D20 = −48.1 (c 1.10, CH2Cl2)Absolute configuration: (2R,3S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(2R,3S)-Methyl 2-methyl-3-(p-methoxyphenylamino)-3-(2′,3′-dimethoxyphenyl)propanoateC20H25NO5[α]D20 = −53.2 (c 2.01, CH2Cl2)Absolute configuration: (2R,3S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(2R,3S)-Methyl 2-methyl-3-(p-methoxyphenylamino)-3-(2′-furyl)-propanoate 5eC16H19NO4[α]D20 = −47.9 (c 1.10, CH2Cl2)Absolute configuration: (2R,3S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
(2R,3S)-Methyl 2-methyl-3-(p-methoxyphenylamino)-3-(2′-thienyl)-propanoateC16H19NO3S[α]D20 = −45.6 (c 1.06, CH2Cl2)Absolute configuration: (2R,3S)Source of chirality: 1-phenylimidazolidin-2-thione induced Mannich reactions
