Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Patent
1997-11-03
1999-07-27
Nazario-Gonzalez, Porfiro
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
556 11, 556 12, 502103, 502117, 526160, 526943, C07F 1700, C07F 700
Patent
active
059292660
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to organometallic, chiral compounds useful in asymmetric synthesis, to processes for preparing said compounds and to a method of using them in industrial processes to produce chiral products.
Various organometallic, chiral compounds are known for asymmetric synthesis (such as from DE4218199).
The present invention provides a chiral, organometallic compound which, at a molecular level, has no C2 symmetry and comprises a carbon to carbon bond joining a chiral carbon atom to a carbon atom of a cyclopentadiene ring that is non-symmetrically substituted. By having a cyclopentadienyl ring that is not symmetrically substituted the organometallic compound possesses planar chirality and by having a chiral group attached to the non-symmetrically substituted cyclopentadiene ring the faces of the cyclopentadiene are diastereotopic. Also, once complexed to the metal of the organometallic compound, the non-symmetrically substituted cyclopentadiene ring provides two control elements for enantioinduction.
In one aspect the present invention provides a compound of formula (I), wherein X.sup.1 and X.sup.2 are, independently, groups which are removable during a chemical reaction; M is titanium, zirconium or hafnium; and (a) R.sup.8 and R.sup.11 are hydrogen; R.sup.1 and R.sup.2 are different and are trialkylsilyl, alkyl, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl; or R.sup.1 and R.sup.2 join to form an asymmetrically substituted C.sub.3-8 cycloalkyl, C.sub.3-8 cycloalkenyl or C.sub.3-8 heterocyclyl ring optionally substituted with hydroxy, trialkylsilyl, alkyl, alkoxy, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl; R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are the same or different and are selected from the substituents already recited for R.sup.1 ; R.sup.4, R.sup.5, R.sup.6 and R.sup.7 may also be, independently, hydrogen; or, one or more of R.sup.3 and R.sup.4, R.sup.4 and R.sup.7 or R.sup.5 and R.sup.6 join to form an optionally substituted saturated or unsaturated ring optionally comprising one or more heteroatoms; or R.sup.3, R.sup.4 or R.sup.7 joins with R.sup.5 to form an optionally substituted C.sub.1-3 alkyl or optionally substituted silyl bridge; or (b) R.sup.3 and R.sup.8 or R.sup.1, R.sup.3 and R.sup.8 join to form an optionally substituted non-aromatic ring system optionally comprising one or more heteroatoms; or R.sup.1 and R.sup.2 are different and are hydrogen, trialkylsilyl, alkyl, aryl, arylalkyl, aryloxyalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl or heteroaryloxyalkyl; one of R.sup.4 and R.sup.11 must be hydrogen the other being selected from the substituents already recited for R.sup.2 apart from hydrogen; R.sup.5, R.sup.6 and R.sup.7 are the same or different and are selected from the substituents already recited for R.sup.2 ; or, one or more of R.sup.4 or R.sup.11 (whichever is not hydrogen) and R.sup.7 or R.sup.5 and R.sup.6 join to form an optionally substituted saturated or unsaturated ring optionally comprising one or more heteroatoms; or R.sup.3, R.sup.7 or R.sup.4 or R.sup.11 (whichever is not hydrogen) joins with R.sup.5 to form an optionally substituted C.sub.1-3 alkyl bridge or optionally substituted silyl bridge.
Alkyl groups and the alkyl part of alkoxy groups have straight or branched chains. They preferably contain from 1 to 10, especially 1 to 6 (for example 1 to 4) carbon atoms, and are, for example, methyl, ethyl, iso-propyl, tert-butyl or n-hexyl. Alkyl and alkoxy groups are optionally substituted, especially optionally substituted by trialkylsilyl or alkoxy.
Aryl includes naphthyl but is preferably phenyl.
Trialkylsilyl groups are especially C.sub.1-8 alkyl.sub.3 Si, for example (CH.sub.3).sub.3 Si.
Cycloalkyl and cycloalkenyl rings preferably contain from 3 to 8, especially from 3 to 6, carbon atoms. They ar
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Bell Jane Louise
Jones Raymond Vincent Heavon
Standen Michael Charles Henry
Whitby Richard John
Nazario-Gonzalez Porfiro
Zeneca Limited
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