Ein Beitrag zur Synthese neuer chiraler Phosphanliganden / Synthesis of a New Chiral Phosphine Ligand

Abstract

X -R ay, Chiral Phosphine, Nickel-Phosphine ComplexThe new chiral diphosphine 2 was synthesized from mucochloric acid. The structure o f the NiLcom plex 7 was determ ined by single crystal X-ray analysis. 7 crystallizes in the orthorhom bic space group P 2 ,2 |2 |. The lattice constants (at 180 K) are: a -914.1(2); b = 1422.0(3); c -4112.5(10) pm. N il 0,5792(1) 0,0959(1) 0,1174(1) 0.022(1) 11 0,5638(1) -0 ,0 7 4 7 (1 ) 0,1324(1) 0.034(1) 12 0,7326(1) 0,0690(1) 0,0677(1) 0.035(1) P l 0,4500(2) 0,1258(1) 0.1602(1) 0.020(1) P2 0,5844(2) 0,2433(1) 0,1055(1) 0.020(1) C I 0,4363(8) 0,2539(5) 0.1622(2) 0,020(2) C 2 0,4879(8) 0,3041(5) 0,1378(2) 0,018(2) C3 0,4683(8) 0,4087(5) 0.1451(2) 0,021(2) C 4 0,3669(9) 0,3180(6) 0,1862(2) 0,027(2) O l 0.3907(6) 0,4527(4) 0,1209(1) 0,022(2) 0 2 0,3838(6) 0,4069(4) 0,1754(1) 0,029(2) 0 3 0,3059(8) 0,3009(5) 0,2115(1) 0,040(2) C5 0,4018(9) 0,5563(5) 0,1204(2) 0,024(2) C 6 0,3258(9) 0,5876(6) 0,0892(2) 0.026(2) C 7 0,3219(11) 0,6945(6) 0,0885(2) 0,035(3) C8 0,2523(10) 0,7382(6) 0,1189(2) 0,036(3) C 9 0,3349(11) 0,7066(6) 0,1492(2) 0,035(3) CIO 0,3354(9) 0,5993(6) 0,1504(2) 0,029(2) C l l 0,3884(11) 0,5441(6) 0,0582(2) 0,037(3) C12 0,5367(11) 0,5815(7) 0,0488(2) 0,048(3) C13 0,2779(14) 0,5577(8) 0,0291(2) 0,055(4) C 14 0,2657(13) 0,7480(6) 0,1792(2) 0.047(3) C15 0,5317(8) 0,0948(5) 0,1988(2) 0,021(2) C 16 0,4893(11) 0,0129(7) 0,2150(2) 0.035(3) C17 0,5609(12) -0 ,0 1 0 7 (7 ) 0,2439(2) 0,042(3) C 18 0,6714(12) 0,0420(8) 0.2554(2) 0,045(4) C 19 0.7170(10) 0,1227(7) 0.2394(2) 0.038(3) C 20 0,6450(9) 0,1482(7) 0.2113(2) 0,030(3) C21 0,2618(9) 0,0860(6) 0,1599(2) 0.027(3) C22 0.2058(10) 0,0484(7) 0,1311(3) 0.040(3) C23 0.0583(13) 0,0189(8) 0,1303(4) 0.066(5) Tab. I. (Fortsetzung).

The Novel Chiral 2(5H)-Furanone Sulfones Possessing Terpene Moiety: Synthesis and Biological Activity

“…In the initial step, 3,4-dihalo-2(5 H )-furanones 3 – 6 were obtained from acid-catalyzed reactions of commercially available mucochloric 1 and mucobromic 2 acids with l -menthol and l -borneol [ 56 , 60 , 63 , 64 , 65 , 66 ] ( Scheme 1 ). Compounds 3 – 6 were firstly synthesized as 1:1 mixtures of diastereomers that differ in the configuration of the C-5 atom of the γ-lactone ring.…”

“…5( S )-3,4-Dichloro-5-[(1 R ,2 S ,5 R )-2-isopropyl-5-methylcyclohexyloxy]-2(5 H )-furanone ( 3a ) [ 60 , 63 ], 5( S )-3,4-dibromo-5-[(1 R ,2 S ,5 R )-2-isopropyl-5-methylcyclohexyloxy]-2(5 H )-furanone ( 4a ) [ 64 ], 5( S )-3,4-dichloro-5-[(1 S ,2 R ,4 S )-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yloxy]-2(5 H )-furanone ( 5a ) [ 56 , 65 ], 5( S )-3,4-dibromo-5-[(1 S ,2 R ,4 S )-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yloxy]-2(5 H )-furanone ( 6a ) [ 66 ], 5( S )-3-chloro-5-[(1 R ,2 S ,5 R) -2-isopropyl-5-methylcyclohexyloxy]-4-[4-methylphenylsulfanyl]-2(5 H )-furanone ( 7 ) [ 60 ], 5( S )-3-chloro-4-[(4-chlorophenyl)sulfanyl]-5-[(1 S ,2 R ,4 S )-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yloxy]-2(5 H )-furanone ( 14 ) [ 85 ], 5( S )-3-chloro-5-[(1 R ,2 S ,5 R )-2-isopropyl-5-methylcyclohexyloxy]-4-[4-methylphenylsulfonyl]-2(5 H )-furanone ( 19 ) [ 60 ], and 5( S )-3-chloro-4-[(4-chlorophenyl)sulfonyl]-5-[(1 S ,2 R ,4 S )-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yloxy]-2(5 H )-furanone ( 26 ) [ 85 ] were synthesized according to the known methods.…”