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1. A process for preparing an optically active bisphosphinylalkanes of formula (I)wherein
R1 and R2 identically are a straight-chain, branched, or cyclic alkyl radical which has up to 12 carbon atoms and is optionally substituted with one or more identical or different substituents selected from the group consisting of halogen, C6-C12-aryl, NR5R6, NHR7, OR8, and aryl radicals having from 6 to 12 carbon atoms and optionally substituted with one or more identical or different substituents selected from the group consisting of C1-C6-alkyl, halogen, C6-C12-aryl, NR5′R6′, NHR7′, and OR8′; or together define an aliphatic ring or bicycle having from 4 to 12 ring members and is optionally substituted with one or more substituents selected from the group consisting of halogen, oxo, C6-C12-aryl, C1-C10-acyl, and C1-C10-sulfonyl, and optionally comprises one or more heteroatoms O or NR9; R3 and R4 identically or differently are each a straight-chain, branched, or cyclic alkyl radical having up to 12 carbon atoms or an aryl radical having from 6 to 12 carbon atoms, each of which is optionally substituted with one or more identical or different substituents selected from the group consisting of C1-C12-alkyl, halogen, NR5″R6″, NHR7″, OR8″, sulphonyl, C(O)OR14, and C(O)NR14′R14″; R5, R6, R5′, R6′, R5″, and R6″are, independently of one another, C1-C12-alkyl or C6-C12-aryl; R7 to R7″are C1-C10-acyl or C1-C10-sulfonyl; R8 to R8″are C1-C12-alkyl or C6-C12-aryl; R9 is C1-C12-alkyl, C6-C12-aryl, C1-C10-acyl, or C1-C10-sulfonyl; R14, R14′ are hydrogen, C1-C12-alkyl, C6-C12-aryl, or C7-C17-aralkyl; R14″ is C1-C12-alkyl, C6-C12-aryl, or C7-C17-aralkyl; and * is an asymmetrically substituted carbon atom;comprising
a) reacting a diol of formula (II) wherein R1 and R2 are as defined in formula (I), to form a compound of formula (III) wherein R1 and R2 are as defined in formula (I), and both Z together in formula (III) form a structural fragment selected from group consisting of —O—S(O)2—O—, —O—P(O)(OR15)2—O—, —O—C(O)—O—, and —O—C(O)—C(O)—O—, wherein R15 is C1-C12-alkyl, C7-C17-aralkyl, or C6-C12-aryl; b) reacting the compound of formula (III) obtained in a) with a phosphine oxide of formula (IV) wherein R3 and R4 are as defined in formula (I), in the presence of a base which is capable of deprotonating said phosphine oxide of formula (IV), to form a racemic 1,2-trans-configured-bis(phosphine oxide) of formula (V) wherein R1, R2, R3, and R4 are as defined in formula (I); c) resolving the racemic-bis(phosphine oxide) of formula (V) obtained in b) to give an optically active-bis(phosphine oxide) of formula (V*) wherein R1, R2, R3, and R4 are as defined in formula (I), and * is an asymmetrically substituted carbon atom, and d) reducing the compound of formula (V*) obtained in c) to give the compound of formula (I). |
