| Record 3388 View: Standard | Glossary HistCite Guide |
|
Author(s): GIARDELLO MA; CONTICELLO VP; BRARD L; SABAT M; RHEINGOLD AL; STERN CL; MARKS TJ
Title: CHIRAL ORGANOLANTHANIDES DESIGNED FOR ASYMMETRIC CATALYSIS - SYNTHESIS, CHARACTERIZATION, AND CONFIGURATIONAL INTERCONVERSIONS OF CHIRAL, C-1-SYMMETRICAL ORGANOLANTHANIDE HALIDES, AMIDES, AND HYDROCARBYLS
Source: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 116 (22): 10212-10240
Date: 1994 NOV 2
Document Type: Journal : Review
DOI:
Language: English
Comment:
Address: NORTHWESTERN UNIV, DEPT CHEM, EVANSTON, IL 60208 USA.
UNIV DELAWARE, DEPT CHEM, NEWARK, DE 19716 USA. Reprint:
E-mail:
Author Keywords:
KeyWords Plus: ANSA-METALLOCENE DERIVATIVES; TRANSITION-METAL COMPLEXES; HIGHLY
REACTIVE ORGANOLANTHANIDES; BRIDGED TETRAHYDROINDENYL LIGANDS; ZIEGLER-
NATTA POLYMERIZATION; X-RAY STRUCTURE; ORGANOACTINIDE COORDINATIVE
UNSATURATION; FUSED CYCLOPENTADIENYL LIGAND; OPTICALLY-ACTIVE ENAMINES;
UNPROTECTED AMINO OLEFINS
Abstract: This contribution describes the synthesis, structural systematics, absolute configurations, and structural interconversions of a series of C-1-symmetric lanthanide chloro, hydrocarbyl, and amide complexes/precatalysts based on chiral chelating Me(2)Si(eta(5)- Me(4)C(5)) (eta(5)-C(5)H(3)R*)(2-) ligands [Me(2)SiCp''(R*Cp)](2-), where R* = (+)-neomenthyl, (-)-menthyl, and (-)-phenylmenthyl. The ligands are prepared in three steps from known chiral cyclopentadienes. Metalation of the chiral dienes followed by condensation with Me(4)C(5)Si(CH3)(2)Cl and in situ lithiation provides the dianions in nearly quantitative yield. Transmetalation of the lithiated ligands with anhydrous lanthanide trichlorides followed by ambient temperature ether workup provides Me(2)SiCp''(R*Cp)LnCl(2)Li(OEt(2))(2) complexes in high yield. For (R)-Me(2)SiCp'' [(+)-neomenthylCp]Lu(mu-Cl)(2)Li(OEt(2))(2): space group P2(1)2(1)2(1); a = 12.240(2), b = 12.876(2), and c = 24.387(5) Angstrom, (24 degrees C); Z = 4; R(F) = 0.0509. As established by NMR and circular dichroism, the diastereomerically pure chloro complexes can be epimerized in appropriate donor solvents to afford mixtures of (R)- and (S)- configurational isomers with the isomer ratio dependent on solvent, R*, and lanthanide ion. Selective epimerization allows enrichment in either antipode with diastereomerically pure complexes obtained in a single recrystallization. Li+ sequestering crown ethers inhibit epimerization. The temperature dependence of the (R) reversible arrow (S) equilibrium constant in THF yields Delta H = 1.7 +/- 0.3 kcal/mol and Delta S 3.6 +/- 0.8 eu for Me(2)SiCp''[(+)-neomenthylCp)Lu(mu-Cl)(2)Li(OEt(2))(2) and Delta H = 4.8 +/- 0.5 kcal/mol and Delta S = 13.4 +/- 0.5 eu for Me(2)SiCp''[(-)-menthylCp]Sm(mu-Cl)(2)Li(OEt(2))(2). The mechanism is proposed to involve reversible ring detachment to an intermediate LiCpR* complex. Alkylation or amidation with ME(SiMe(3))(2) (M = Li or K, E = CH; M = Na or K, E = N) yields the corresponding chiral hydrocarbyls and amides in high yield. For (R/S)-Me(2)SiCp''[(+)- neomenthylCp]YCH(SiMe(3))(2): space group P2(1); a 19.178(4), b = 8.736(1), and c = 21.391(5) Angstrom; beta = 97.62(;); Z = 4; R(F) = 0.071. For (R)-Me(2)SiCp''[(-)-menthylCp]SmCH(SiMe(3))(2) space group P1; a = 8.993(3), b = 12.738(2), and c 16.549(4) Angstrom; alpha = 86.04(2)degrees; beta = 82.81(2)degrees, gamma = 72.91(2)degrees; Z = 2; R(F) = 0.026. For (R)-Me(2)SiCp''[(-)-menthylCp]YCH(SiMe(3))(2); space group P2(1); a = 12.319(3), b = 15.707(4), and c = 18.693(5) Angstrom; beta 91.59)(2)degrees; Z = 4; R(F) = 0.054. For (S)-Me(2)SiCp''[(+)- neomenthylCp]SmN(SiMe(3))(2): space group P2(1); a = 9.122(2), b = 10.112(3), and c = 18.478(3) Angstrom; beta = 90.58(2)degrees; Z = 2; R(F) = 0.029, For (S)-Me(2)SiCp''[(-)-menthylCp]SmN(SiMe(3))(2): space group P2(1)2(1)2(1); a = 10.217(3), b = 19.103(6), and c = 19.456(7) Angstrom; Z = 4; R(F) = 0.044. For (R)-Me(2)SiCp''[(-)- menthylCp]YN(SiMe(3))(2); space group P1; a = 8.937(3), b = 12,397(6), and c = 16.673(7) Angstrom; alpha = 85.53(2)degrees, beta = 82.17(2)degrees, gamma = 74.78(2)degrees Z = 2; R(F) = 0.065. The preferred planar chiral configurations of these complexes can be largely understood on the basis of significant, crystallographically identifiable, nonbonded interactions between R* and the remainder of the molecule. The hydrocarbyl and amide complexes are configurationally stable in toluene at 60 degrees C for many hours but undergo facile epimerization in the presence of primary alkyl amines, presumably via reversible Cp protonation/detachment. The hydrocarbyl complexes undergo rapid hydrogenolysis at ambient temperature, with retention of configuration, to yield the corresponding hydrides.
Cited References: ALHASHIMI S, 1978, J ORGANOMET CHEM, V153, P253 ATWOOD JL, 1978, J CHEM SOC CHEM COMM, P140 BERCAW JE, 1986, ORGANOMETALLICS, V5, P443 BONDI A, 1964, J PHYS CHEM-US, V68, P441 BOSNICH B, 1986, NATO ASI SERIES E, V103 BROCK CP, 1991, J AM CHEM SOC, V113, P9811 BROENE RD, 1993, J AM CHEM SOC, V115, P12569 BROWN CA, 1974, J ORG CHEM, V39, P3913 BRUNNER H, 1971, Z NATURFORSCH B, V26, P1220 BRUNNER H, 1974, ANGEW CHEM INT EDIT, V13, P810 BRUNNER H, 1975, J ORGANOMET CHEM, V87, P223 BRUNNER H, 1976, J ORGANOMET CHEM, V104, P347 BRUNNER H, 1976, J ORGANOMET CHEM, V120, P239 BRUNNER H, 1988, SYNTHESIS-STUTTGART, P645 BRUNNER H, 1989, ANGEW CHEM INT EDIT, V28, P1521 BURGER BJ, 1990, J AM CHEM SOC, V112, P1566 BURGER P, 1989, J ORGANOMET CHEM, V378, P153 BURSTEN BE, 1985, INORG CHIM A-F-BLOCK, V110, P153 CARNALL WT, 1978, ORGANOMETALLICS F EL, PCH9 CESAROTTI E, 1978, J ORGANOMET CHEM, V162, P297 CESAROTTI E, 1981, J ORGANOMET CHEM, V216, P87 CESAROTTI E, 1984, J CHEM SOC DALTON, P653 CESAROTTI E, 1985, J ORGANOMET CHEM, V286, P343 COLLINS S, 1990, ORGANOMETALLICS, V9, P2695 COLLINS S, 1991, ORGANOMETALLICS, V10, P2061 COLLINS S, 1991, ORGANOMETALLICS, V10, P2349 CONTICELLO VP, UNPUB COUGHLIN EB, 1992, J AM CHEM SOC, V114, P7606 COUTURIER S, 1980, J ORGANOMET CHEM, V195, P291 COWLEY AH, 1981, SYN REACT INORG MET, V11, P591 CRAMER RE, 1989, ORGANOMETALLICS, V8, P1192 DAY CS, 1982, ORGANOMETALLICS, V1, P998 DENHAAN KH, 1986, ORGANOMETALLICS, V5, P1726 DEWEY MA, 1990, ORGANOMETALLICS, V9, P1351 DORMOND A, 1983, TETRAHEDRON LETT, V24, P3087 EDELSTEIN N, 1985, FUNDAMENTAL TECHNOLO, PCH7 ERKER G, 1989, ANGEW CHEM INT EDIT, V28, P628 ERKER G, 1991, J AM CHEM SOC, V113, P7594 EVANS WJ, 1983, J AM CHEM SOC, V105, P1401 EVANS WJ, 1987, J AM CHEM SOC, V109, P4292 EVANS WJ, 1993, ORGANOMETALLICS, V12, P2618 EWEN JA, 1984, J AM CHEM SOC, V106, P6355 EWEN JA, 1987, J AM CHEM SOC, V109, P6544 FALK H, 1965, MONATSH CHEM, V96, P1065 FALK H, 1965, MONATSH CHEM, V96, P1081 FALLER JW, 1980, J AM CHEM SOC, V102, P5396 FALLER JW, 1982, J ORGANOMET CHEM, V226, P251 FALLER JW, 1983, J AM CHEM SOC, V105, P3893 FALLER JW, 1984, ORGANOMETALLICS, V3, P927 FALLER JW, 1989, J AM CHEM SOC, V111, P1937 FALLER JW, 1989, TETRAHEDRON LETT, V30, P1769 FENDRICK CM, 1984, ORGANOMETALLICS, V3, P819 FENDRICK CM, 1988, ORGANOMETALLICS, V7, P1828 FRAGALA IL, 1989, 197TH NAT M AM CHEM GAGNE MR, 1989, J AM CHEM SOC, V111, P4108 GAGNE MR, 1990, ORGANOMETALLICS, V9, P1716 GAGNE MR, 1992, J AM CHEM SOC, V114, P275 GIARDELLO MA, 1992, ENERGETICS ORGANOMET, P35 GIARDELLO MA, 1994, J AM CHEM SOC, V116, P10241 GLADYSZ JA, 1992, CHEM REV, V92, P739 GUTMANN S, 1989, J ORGANOMET CHEM, V369, P343 HALTERMAN RL, 1986, TETRAHEDRON LETT, V27, P1461 HALTERMAN RL, 1987, J AM CHEM SOC, V109, P8105 HALTERMAN RL, 1987, THESIS U CALIFORNIA HALTERMAN RL, 1988, ORGANOMETALLICS, V7, P883 HALTERMAN RL, 1992, CHEM REV, V92, P965 HARRISON KN, 1992, J AM CHEM SOC, V114, P9220 HART AJ, 1974, J ORGANOMET CHEM, V72, PC19 HAZIN PN, 1987, ORGANOMETALLICS, V6, P23 HE MY, 1985, J AM CHEM SOC, V107, P641 HEERES H, 1990, THESIS U GRONINGEN G HEERES HJ, 1988, J CHEM SOC CHEM COMM, P962 HEERES HJ, 1988, ORGANOMETALLICS, V7, P2495 HEERES HJ, 1989, ORGANOMETALLICS, V8, P2637 HEERES HJ, 1990, RECL TRAV CHIM PAY B, V109, P226 JEFFERY J, 1978, J CHEM SOC CHEM COMM, P1081 JESKE G, 1985, J AM CHEM SOC, V107, P8091 JESKE G, 1985, J AM CHEM SOC, V107, P8103 JESKE G, 1985, J AM CHEM SOC, V107, P8111 JORGENSEN CK, 1971, MODERN ASPECTS LIGAN, PCH28 KAMINSKY W, 1985, ANGEW CHEM INT EDIT, V24, P507 KAMINSKY W, 1986, MAKROMOL CHEM-M SYMP, V3, P377 KOGA N, 1988, J AM CHEM SOC, V110, P108 KROW G, 1970, TOP STEREOCHEM, V5, P31 LAPPERT MF, 1981, J CHEM SOC CHEM COMM, P1191 LAPPERT MF, 1981, J CHEM SOC DALTON, P814 LAPPERT MF, 1983, J CHEM SOC CHEM COMM, P69 LEBLANC JC, 1976, J ORGANOMET CHEM, V120, P65 LEBLANC JC, 1977, NOUV J CHIM, V1, P211 LEBLANC JC, 1978, J ORGANOMET CHEM, V148, P171 LINDSAY C, 1990, ORGANOMETALLICS, V9, P2594 MAGINN RE, 1963, J AM CHEM SOC, V85, P672 MANASTYRSKYJ S, 1963, INORG CHEM, V2, P904 MANZER L, 1976, INORG CHEM, V14, P2567 MANZER LE, 1978, J AM CHEM SOC, V100, P8068 MARKS TJ, 1978, PROG INORG CHEM, V24, P51 MARTIN GC, 1989, ORGANOMETALLICS, V8, P2968 MAUERMANN H, 1985, ORGANOMETALLICS, V4, P200 MCILWRIC.CR, 1973, J PHYS E SCI INSTRUM, V6, P1208 MEYER G, 1989, INORG SYNTH, V25, P146 MISLOW K, 1984, J AM CHEM SOC, V106, P3319 MOESELER R, 1976, Z NATURFORSCH B, V31, P892 MOISE C, 1975, J AM CHEM SOC, V97, P6272 MOLANDER GA, 1992, J AM CHEM SOC, V114, P3123 MOLANDER GA, 1992, J ORG CHEM, V57, P3266 MOLANDER GA, 1992, J ORG CHEM, V57, P6347 MOORE JW, 1981, KINETICS MECHANISM, PCH2 MORIARTY KJ, 1989, ORGANOMETALLICS, V8, P1512 MORRISON JD, 1985, ASYMMETRIC SYNTHESIS, V5 NOYORI R, 1989, CHEM SOC REV, V18, P187 NOYORI R, 1994, ASYMMETRIC CATALYSIS OPPOLZER W, 1981, TETRAHEDRON LETT, V22, P2545 OPPOLZER W, 1984, ANGEW CHEM INT EDIT, V23, P876 PAQUETTE LA, 1986, TETRAHEDRON LETT, V27, P5599 PAQUETTE LA, 1989, ORGANOMETALLICS, V8, P1506 PAQUETTE LA, 1989, ORGANOMETALLICS, V8, P1707 PARSHALL GW, 1992, HOMOGENEOUS CATALYSI, PCH2 PFALTZ A, 1993, ACCOUNTS CHEM RES, V26, P339 RAUSCH MD, 1984, J ORGANOMET CHEM, V265, P241 RAUSCH MD, 1986, ORGANOMETALLICS, V5, P1281 RHEINGOLD AL, 1992, ORGANOMETALLICS, V11, P1869 RIEGER B, 1990, MACROMOLECULES, V23, P3559 RIEGER B, 1992, J ORGANOMET CHEM, V428, PC33 ROLL W, 1987, J ORGANOMET CHEM, V322, P65 ROLL W, 1990, ANGEW CHEM INT EDIT, V29, P279 SAKAKURA T, 1991, J CHEM SOC CHEM 0101, P40 SCHAFER A, 1987, J ORGANOMET CHEM, V328, P87 SCHMIDBAUR H, 1968, CHEM BER, V101, P3556 SCHUMANN H, 1984, ANGEW CHEM INT EDIT, V23, P522 SCHUMANN H, 1986, ORGANOMETALLICS, V5, P1296 SCHWEMLEIN H, 1983, J ORGANOMET CHEM, V254, P69 SCOTT JW, 1989, TOP STEREOCHEM, V19, P209 SHANNON RD, 1976, ACTA CRYSTALLOGR A, V32, P751 SLOAN TE, 1981, TOP STEREOCHEM, V12, P1 STANLEY K, 1975, J AM CHEM SOC, V97, P6598 STERN D, 1990, J AM CHEM SOC, V112, P9558 TAKAHASHI T, 1991, J AM CHEM SOC, V113, P8564 TANI K, 1982, J CHEM SOC CHEM COMM, P600 TANI K, 1984, J AM CHEM SOC, V106, P5208 TATSUMI K, 1987, J AM CHEM SOC, V109, P3195 TESSIERYOUNGS C, 1986, INORG SYNTH, V24, P95 THOMPSON ME, 1984, PURE APPL CHEM, V56, P1 TILLEY TD, 1981, INORG CHEM, V20, P3267 WATSON PL, 1981, INORG CHEM, V20, P3271 WATSON PL, 1982, J AM CHEM SOC, V104, P337 WATSON PL, 1982, J AM CHEM SOC, V104, P6471 WATSON PL, 1983, ACS SYM SER, V212, P459 WATSON PL, 1985, ACCOUNTS CHEM RES, V18, P51 WAYDA AL, 1980, INORG CHEM, V19, P2190 WHITESELL JK, 1982, J CHEM SOC CHEM COMM, P989 WIESENFELDT H, 1989, J ORGANOMET CHEM, V369, P359 WILD FRW, 1985, J ORGANOMET CHEM, V228, P63 WILD FRWP, 1982, J ORGANOMET CHEM, V232, P233 WILD FRWP, 1985, J ORGANOMET CHEM, V288, P63 WILLOUGHBY CA, 1992, J AM CHEM SOC, V114, P7562 |