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Leo Armand Paquette 2011-08-20 Baran GM R.A. Rodriguez Leo Armand Paquette 2011-08-20 Born in Worcester, Mass., July 15, 1934 Syntheses Discussed B.S., Holy Cross College, 1956 Ph.D., MIT, 1959 synthesis of azasteroids and regioselectivity in Baeyer-Villiger (Adv. Norman A. Nelson) Upjohn, medicinal chemist, 1959-63 Prof. Ohio State University, 1969-present Honors and Awards [4]peristylane Elassovalene [22](1,5)Cyclo- Dodecahedron 1965 Alfred P. Sloan Fellow ctatetraenophane 1971 Morley Medalist Cleveland Section Me 1976 Guggenheim Fellow OH O H 1979 Columbus Section Award Me H H Me 1980 Senior Research Award, OSU 1981 Kimberly Professorship in Chemsitry Me Me 1987 Arthur C. Cope Scholar Me Me Me 1984 National Award for Creative Work Me Me OAc Me Salsolene oxide in Synthetic Organic Chemistry Pentalene 1989 Senior Humboldt Fellow 4aβ, 10β-doladiol acetate 1990 Sullivant Medal, OSU highest honor Me Me O 1992 Awardee of the Japanese Society for Me the Promotion of Science HO O Me 1992 Ernest Guenther Award Me Me O Me 2002 S.T. Li Prize Science and Technology Me Me H O O O OMe 3 1390 publications (111 reviews) HO 42 patents MeO (-)-Austalide B C(3) OH α; C(3) OH β 17 books 38 book chapters Timeline: Career in review Natural Product Synthesis 1979-present Gymnomitrol and Isocomene 1979 Research interests 55 total syntheses to date Heterocyclic chemistry Hydrocarbon chemistry Natural product synthesis Hydrocarbons 1974-1990 Dodecahedrane 1982 Synthetic methodology Catalytic asymmetric methods Heterocyclic chemsitry 1962-1975 Organoetallic chemistry Azepine 1962 Oxy-Cope RR 1978-2000 Organosulfur reagents Ag(I) cat. RR di-π−methane RR Squarate esters Indium reagents 1970-75 1975-1984 1993-97 1995-2000 Postdoctoral Researchers from the Paquette group: 1962 1968 Steven Ley (1972-1974) 1975 1981 1987 1993 2000 2006 2011 Louis Barriault (1997-1999) Organosulfur 1964-74 Silicon chemistry (-)-polycarvernoside A α-Halosulfones 1964 1977-1984 Polyspiro tetrahydrofurans 1981-2004 Baran GM R.A. Rodriguez Leo Armand Paquette 2011-08-20 Heterocyclic and Carbocycle Chemistry 1962-1975 MeO Upjohn and OSU N N Syntheses and derivatives: Syntheses and derivatives: MeO JACS 1962, 84, 4987 JACS 1965, 87, 1718 Azasemibullvalene Semibullvalene JACS 1963, 85, 4053 JACS 1965, 87, 3417 Azabullvalene Bullvalene N O 1969 H JACS 1964, 86, 4092 JACS 1968, 90, 6148 1967 Azepine JACS 1964, 86, 4096 Oxepin JACS 1972, 94, 6751 e.g. phenol and chloramine A Synthetic Entry into the Azasemibullvalene System Photochemistry of Carbocycles O Me Me Me Me Me ClO SN O O Me 2 H Me ClO2SN C O Me Me Me Me hv acyclic Me hv NSO2Cl α,β-cyclopropane Me Me Me Me H ester O Me Me 1/4 products trans-Bicyclo[6.1.0]nonan-2-ones 2,3 Homotropone O O JACS 1969, 91, 7108 Me JACS 1967, 89, 5633 Me Me Me ClO2SN HN + - Me NaOH 1. Me3O BF4 Me Me Me Me Me Me Me 2. K CO Me 2 3 N Identification of cationic species 1968 (collaboration with Olah) Me The Protonation of Hexamethyl Dewar Benzene and Hexamethylprismane Me Me Me Me MeO in FSO3H−SbF5−SO2 "magic acid" Me JACS 1969, 91, 6107; JACS 1967, 89, 5480; Me JACS 1975, 97, 6124; JACS 1970, 92, 4338 Me Me Me Me Me Me JACS 1968, 90, 7147 Novel aromatics 1976 Me Me Me Me The First 8C-6π Huckeloid System: 1,3,5,7- Tetramethylcyclooctatetraene Dication Protonation of cis-Bicyclo[6.1.0]nona-2,4,6-trienes in superacidic media Me Me JACS 1976, 98, 1267 2 + H Me FSO3H−SO2ClF Me + + Me + −95 °C Me H initial trans cation Me Me JACS 1973, 95, 3386 JACS 1976, 98, 4327 Bis(tetramethylhomocyclopropenyl) Dication Baran GM R.A. Rodriguez Leo Armand Paquette 2011-08-20 Synthetic Methods: 3. di-π-methane RR 1975-80 1. Ramberg-Backlund 1964-74 1989 [3]peristylane Upjohn: Conversion of Mercaptans to Homologous Terminal Olefins HO O OH [O] hv SH SCH2Cl SO2CH2Cl 90% 97% O oxydi-π-methane Tetrahedron 1989, 45, 3099 OH- Cl 4. Silanes 1977-84 S S - cyclopentanone synthesis O O O O O Me Me O 1. PhSO2NHNH2 TMS Cl AlCl3 2. nBuLi + HO SO CH Cl O 2 2 X 3. TMSCl Me Me Me O O JACS 1964, 86, 4383 JOC 1980, 45, 3017 Me Chem. Rev. 1986, 86, 733 SnCl4 RR of α,α-Dichloromethyl Sulfones (silyl cylopropanes) R Cl Me Me Me Me base base -SO2 R CH SO CHCl 2 2 2 R TMS TMS -HCl S -HCl TMS O O JACS 1967, 89, 4487 Me Me Me α−Vetispirene Me Me Me Me 2. Ag I cat. RR 1970-75 Tet.Lett 1982, 23, 3227 Ag Ag Ag Ag+ Diels-Alder equivalents Phenyl Vinyl Sulfoxide as trans-1-(Phenylsulfonyl)-2-(TMS)ethylene as (AgBF ) H 4 Acetylene Equivalent Ethylene Equivalent H vs >150 °C w/o Ag (I) O SO2Ph H H PhS Br Br H Ag+ TMS H H MeLi H * cis found to be less reactive 80% (AgBF4) via ene-type 40 °C quant. clean JACS 1978, 100, 1597 JACS 1980, 102, 4976 non-conjugated triene JACS 1971, 93, 1288; JACS 1980, 102, 637 • Indium 1995 • Zr 2002 Baran GM R.A. Rodriguez Leo Armand Paquette 2011-08-20 Men of learning in ancient Greece took especial concern for "the putting together of cosmic figures.' their regular polyhedra whose mathematical elegance inspired considerable wonder. The heritage of that wonder inevitably passed into the realm of synthetic organic chemistry and attracted the practitioners of this science to apply their skills to the construction from carbon and hydrogen of such strained molecules... A journey to dodecahedron: selected syntheses of hydrocarbons JACS, 1983, 105, 4113 T e molecular modeling shows t • r a serious nonbonded steric strain h X e d r [3] peristylane [4] peristylane [5] peristylane o R n [4] peristylane Eaton and Muller , R "triaxane" 1 top view 9 8 9 , 4 5 , 3 H O 0 top view octahedrane decahedrane 9 1. SeO2 H dodecahedrane 9 PhH, Δ mCPBA [8 faces] [10 faces] [12 faces] 2. Al2O3, H quinoline 98% 2 steps When first synthesized, trixane was viewed predominantly as a chemical curiosity. Ts Ts TS quant hv It was initially named "triaxane" in an effort to capture the C symmetry of its 3v 1. BF3, O + acetone 1.eth.gly., H O tetracyclic framework and to depict that the cyclopropane ring rests on three Et3SiH O O 2. Li, EtNH O HIO4, axial pillars fixed to a cyclohexane chair. 2 2. TsCl, py 3.H O+ 10%aq After successful preparation of one of these hydrocarbons, Eaton named it 3. LAH, Δ 3 69% 3 steps MeOH "peristylane" after a Greek word hat alludes to the similarity to "a group of 64% 3 steps 95% Ts columns arranged about an open space in a manner designed to support a roof". Ts Several years later, Garratt and White noted that the top row (vide supra) N OH HO2C Me O O O O hydrocarbons constitutes a series of compounds characterized by the NaOEt, 1. interconnection of a smaller n-memberd ring to one twice the original size at EtONO O alternate carbons of the latter and the community decided to generalize the HO Eaton nomenclature. 77% 2. OH TsOH OH Hypostrophene N I O 1. hv 63% 2 steps [3] peristylane OH OH O O NaK-alloy "triaxane" 2. I2, PPh3 54% quant [5 gram] 1. hv O wurtz-type O MsCl/TEA 0 C; O ° 76% 2. H+,Δ I S rt NO GOOD!! H O Δ Δ I 1. sulfene [3+2] N NHTs N NHTs 85% OH LAH O wurtz N N H 2. NaI 84% SOCl2 H 90% H HO O Cl Cl I I O CO H O CO2H Cl O 80% 2 Br Tet. Lett., 1974, 17, 1615 Baran GM R.A. Rodriguez Leo Armand Paquette 2011-08-20 JACS, 1990, 112, 1258; Tetrahedron, 1981, 37, 4521 B Br A B Br 45 ° A E [22](1,5)Cyclooctatetraenophane The Weiss-Cook reaction: E R E E R O R - 4CO2 E aq. buffer O O O O O + 2 equiv O R E R E R E cis-bicyclo[3.3.0] CO2Me octanedione 1.LAH Br SiO2 E 2. DHP/H+ (10X weight) E E 3.Ph3PBr2 ether, rt O - 4CO2 O pH = 5.6 O O O O 66% 3 steps two-fold + HCl, Br Δ CO Me cation-olefin O 85% 2 E E 92% cyclization 83% 2 equiv E 1. OsO4 2.HO 83% OH TsOH Br H Br O H AgClO E Me Me 4 H 1.LAH 1. H O O O PhH/pentane Br 2.NaH, O HO OH 1.LAH O O CS2, MeI; (COCl)2, 2.NaH, CS Br 2 eq 2 Δ E DMSO MeI; Δ Bu3SnH 70% 2. HCl, Δ 69% 3.TsOH 85% 56% O all mixtures A + all mixtures B NBS 4 eq O AIBN/CCl 4 minor (~ 1:2) major Br Br B Ni(CO)4 H , Pt [3,3] 500 °C 2 DMF EtOAc 34% 40% bicyclo bicyclo Br 2 steps brsm Br A [3.2.1]octane [2.2.2]octane all mixtures JACS, 1979, 101, 4773 Baran GM R.A. Rodriguez Leo Armand Paquette 2011-08-20 Elassovalene Used in studies towards the evaluation of homoaromaticity-special [4.4.4]Propella-2,4,7,9,12-pentaene & [4.4.4]Propellahexaene case of aromaticity in which conjugation is interrupted by a single luche/ sp3 hybridized carbon atom.
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