Stereospecific isomerisation of allylic amines using chiral phosphorus ligands

Prochiral allylamines (I) are stereospecifically isomerized to enamines (II) or imines (III) over a rhodium, iridium or ruthenium catalyst containing at least one chiral phosphine ligand which is a ferrocene derivative (optionally fixed to a polymer) or a bis-steroid derivative. Isomerization of pro...

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Hauptverfasser:	BARTHE, MICHEL, CHAPUIS, CHRISTIAN
Format:	Patent
Sprache:	eng ; fre ; ger
Schlagworte:	ACYCLIC OR CARBOCYCLIC COMPOUNDS APPARATUS THEREFOR CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOIDCHEMISTRY CHEMISTRY GENERAL METHODS OF ORGANIC CHEMISTRY METALLURGY ORGANIC CHEMISTRY PERFORMING OPERATIONS PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL THEIR RELEVANT APPARATUS TRANSPORTING
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Beschreibung
Zusammenfassung:	Prochiral allylamines (I) are stereospecifically isomerized to enamines (II) or imines (III) over a rhodium, iridium or ruthenium catalyst containing at least one chiral phosphine ligand which is a ferrocene derivative (optionally fixed to a polymer) or a bis-steroid derivative. Isomerization of prochiral allylamines of formula (I) into enamines of formula (II) or (if R5 = H) imines of formula (III) is effected using an Ru, Ir or Ru catalyst containing at least one chiral phosphine ligand of formula (IV) or (V): R1, R2 = 1-12C alkyl, 2-12C alkenyl or aryl (optionally substituted by OH), R1 and R2 being different; R3, R4 = H, 1-12C alkyl, 2-12C alkenyl or aryl; R5 = H, 1-8C alkyl or 3-8C cycloalkyl; R6 = 1-8C alkyl or 3-8C cycloalkyl; or NR5R6 = 5- or 6-membered ring or 6-membered ring containing O; X = H or -(A)n-B-P'; n = 0 or 1; A = intercalating group containing at least one of O, S, Si, N and C; B = linking group; P' = organic or inorganic polymer; either (i) Z' = P; R'1 = 1-8C alkyl or phenyl (optionally substituted by 1-3 of T and OT); T = 1-4C alkyl; R'2, R'3, R10, R11 = 1-12C alkyl; 5-12C cycloalkyl (optionally substituted by T or OT); phenyl (optionally substituted by 1-3 R13); or phenyl substituted by (R12)m and (R13)p; R12 = partially or completely fluorinated 1-5C alkyl; R13 = T, OT, SiR'4R'5R'6, halo, SO3M, COOM, PO3M, NR7R8 or NR7R8R9.X; m = 1-3; p = 0-4; m+p = 1-5; R'4-R'6 = 1-12C alkyl or Ph; R7, R8 = H, 1-12C alkyl or Ph; or R7 + R8 = (CH2)4, (CH2)5 or (CH2)2O(CH2)2; R9 = H or T; M = H or alkali metal; Y = anion of monobasic acid; or (ii) Z' = N; R'1 = as in (i); R'2, R'3 = 1-12C alkyl, 5-12C cycloalkyl or phenyl (optionally substituted by 1-3 T); or NR'2R'3 = 5-12 membered ring optionally containing further O or N; R11, R12 = Ph; Q1 = H, F, alkyl, acyl or X'Q5; X' = O or S; Q5 = H, alkyl or aryl; Q2 = H or alkyl; Q3 = H, F, alkyl, aryl, trialkylsilyl or X'Q6; Q6 = H, alkyl, aryl or SO2CF3; Q4 = H, F, alkyl, aryl or Y'Q7; Y' = O, S or trialkylsilyl (sic); Q7 = H, alkyl, aryl or SO2CF3; In (V) the stereochemistry at C-13, C-14 and C-17 may be alpha or beta and the B ring is saturated or contains 2 double bonds.