Baran Group Meeting Lisa M. Barton The Barton Family Tree 3/11/17

Sir Derek H.R. Barton Professor from 1946 until death in 1998 *See Baran Group Meeting, Gutekunst, 2010

Paul De Mayo Severyn Sternhell Samir Z. Zard Jack E. Baldwin D. John Faulkner University of Western Ontario University of Sydney and École polytechnique Imperial College Imperial College Graduate Student 53'–54' CSIRO Graduate Student 79'–83' *See Baran group meeting *See Baran group Graduate Student 58'–60' by Georgiades, 2006 meeting by O'Malley, 2005 Graduate Student 60–65' Graduate Student –65'

David Crich Philip D. Magnus Anthony G.M. Barrett University of Illinois at Derrick L.J. Clive Imperial College Imperial College, Norwestern, Chicago and Wayne State University of Alberta *See Baran group and Colorado State University Graduate Student meeting by Yan, 2013 Graduate Student 73–75' Graduate Student 81'–84', Graduate Student 65'–68' Post Doc 84'–85'

E. W. Warnhoff Gerhard Quinkert Bertram O Fraser–Reid Ezio Rizzardo Robert Vyent Stick William B. Motherwell University of Technical University of Braunschweig University of Waterloo CSIRO University of Western Imperial College and UCL Western Ontario and Goethe University and Duke Post Doc 73'–74' Australia Post Doc 75'–77' Post Doc 54'–56' Post Doc 57'–59' Post Doc 64'–66' Post Doc 73'–75'

Darshan Ranganathan Steven Ley Steve Davies Gerhard Bringmann Jieping Zhu Delhi University and Indian Imperial, Cambridge and Oxford University of Munster and École polytechnique Institute of Technology Trinity College Post Doc 77'–78' Wurzburg Post Doc 91'–92' Post Doc 66'–69' *See Baran group Post Doc 78'–79' meeting by Jorgensen, 2012 Post Doc 74'–75' *Covered in previous group meetings Baran Group Meeting Lisa M. Barton The Barton Family Tree 3/11/17 Samir Z. Zard Synthesis of the Core of Structure Polycyclic Alkaloids SCSOEt 1) AIBN, nBu SnH NBoc 3 • B.Sc. first at the American University of Beirut then at Imperial NBoc MeO O 79% College (1978) 2) TBAF OMe OMe N SCSOEt 93% • Ph.D. at ICSN under Sir Derek Barton (1979-83) N TBS TBS • Director of Research - Exceptional Class at the CNRS and 10%dilauroyl peroxide CO Me Professor of Organic Chemistry at the École polytechnique 3 steps reflux DCE 2 66% MeO (1986-present) NBoc OMe • Recipient of the Organic Chemistry Division of the French H N N Chimcal Socity (1992), Clavel-Lespiau Prize (1995), Rhodia H N TFA reflux H Prize (2000), Dargelos Prize (2006), Novartis Chemistry N N 71% CO M Lectureship (2006-07), Silver Medal of the CNRS (2007) and H 4:1 cis:trans 2 O H MeO e Croix de Chevalier de la Légion d'Honneur (2007) (±)–cis- MeO2C H OMe • Over 47 authorships with Barton including the reduction of xanthates, synthesis of pyrroles, deethyleburnamonine Tett. Lett. 2002, 43, 4683 decarboxylation, deoxygenation, the synthesis of corticosteroids, and multiple radical additions ( )–Matrine ± CO2tBu MeO2C CO2Me O O both pieces 3 steps Xanthates Radical Chemistry in Total Synthesis from commerically + •Xanthates can serve as a reversive radical trap to extend the lifetime of R•, allowing the radical N N N available starting H S material to undergo inter– and intramolecular reactions that would not normally occcur H H H O EtO S S H cat. lauroyl peroxide R benzene S OEt R MeO C CO Me MeO C CO Me MeO C CO Me Peroxide 2 2 2 2 2 2 S Benefits O O O R S R' ' • reagents are cheep H H S EtO R • no metals N N SCSOEt N SCSOEt S R • can be run at high EtOSCS CO2tBu + H H + H H EtO R R concentrations and in water CO2tBu CO2tBu cat. lauroyl peroxide R' • scalable N benzene N 3:1 N • initiators other than peroxides 80% can be used 18% R S S O O O ' • high functional group tolerance S R 30% R • can easily remove with nBu3Sn lauroyl peroxide OEt S OEt 2-propanol R SH 89% heat S MeO C CO Me R OEt MeO2C CO2Me MeO2C CO2Me 2 2 O O O BH3•Me2S; H 1) CF CO H H H 2M HCl, N 3 2 N N reflux 90% Have been used to access: (±)–Matrine H H 2) Barton's H H H H • Bridging rings • heterocyclic structures from α-chloroketones 85% H CO tBu CO2tBu conditions 2 • β-lactam 4 membered ring • alkaloid structures 56% • homodimers • many more Chem. Eur. J. 2006, 12, 6002 N N N 3:1 • Not covered: the use of xanthates as chain-transfer agents in controlled radical polymerization O O 65% O Ang. Chem. Int. Ed. 1998, 37, 1128 Baran Group Meeting Lisa M. Barton The Barton Family Tree 3/11/17 Nitrogen Centered Radicals O O SAr Thiocarbazones O lauroyl peroxide H H 1)TFA H H S N S OTBS MeO OTBS O A N 60% MeO 88% H2N 2) ArSH N S A S Ph H N 80% N Ph H BnO BnO cystalline, made in one step Bu3SnH O O 1)LAH from methylhydrazine, CS2 and AIBN only trans ring junctions observed 66% MeI 14:1 para/ortho 2)DMDO 92% N S HO N HO SO Ar N 65% N N H 2 S MeO H H Ph Ph Ph H SnBu3 1)H2, Pd/C MeO OTBS Ph H H quant Tett. Lett. 1995, 36, 8791 N HO 2) Na/Hg N Oxime Derivatives Ph Fortucine 50% BnO (originally assigned as kirkine) O O

1) NH2OH, HCl O O Bu3SnH 88% Angew. Chem. 2008, 47, 1436 2)BzCl, pyridine N AIBN N N Ph Ph (–)-dendrobine Ph Ph H NHMe Can also be used to open strained ring systems 1) Im2CO OBz 1) Bu3SnH, 2) MeNHOH N AIBN CN Me N 1) NH2OH, HCl 3) BzCl, Et3N 71% OH 2) BzCl, pyridine + H H OH 49% O O 2) aq KOH O CN Me 68% 3) Bu3SnH (+)-trans- AIBN 1) CH Br 89% 3% O vervenol 2 O K2CO3 With hydroxamic acids: 2) Ac2O, pyr Bu3SnH 88% 1) MeNHOH AIBN 2) BzCl, pyridine 1)TMSI, HMDS 1)Co (CO) 60% Et AlCN O N O N 2 8 N 2 2) PhSeBr 2) NMO•H O O O O 77% 2 NM MeBzON 72% ACN e Cl Me H H Me H 3) MCPBA 3) Pd/C, H2 Tetrahedron. 1995, 51, 6517 OAc 60% OAc 51% OAc Use In Total Synthesis 1) NaBH4 O 2) O OTBS BnO 1)NaBH4 Cl pTsOH 1) O 2) PhOC(S)Cl N LDA CH3 O O N O O OTBS DMAP MeONa N Dioxane/ N MeO MeS2CPhN N 60% H H MeOH H2O O H H Me Product MeS2CPhN O Me 3) Bu SnH, H Me H 81% 3 NC OAc NC OAc VAZO 75% based 2) TBSOTf N NC * OH on BnO 83% Quant. NPhCS2Me recovered O diastereomer MeO JACS. 1999,121, 6072 1:1 at indicated center Baran Group Meeting Lisa M. Barton The Barton Family Tree 3/11/17 O O William B. Motherwell Fromation Biaryls Me S R R N –SO Me • B.Sc. and Ph.D. from University of Glasgow under 2 NH James S. Roberts as a Carnegie scholarship holder (1972) • Recieved an ICI Fellowship to conduct independent research at O O the University of Stirling (1972-74) R Me S nBu SnH • Schering–Plough Postdoctoral Fellow with Barton at N 3 AIBN [1,5] Ipso Substiution Imperial College (1975-77) X • Charge de Recherche under Barton at Institut de Chimie des OR Substances Naturelles (ICSN) (1978-83) O O O • Lecturer and Reader at Imperial College (1983-93) R O R Me S Me S • Alexander Williamson Chair of Chemistry at University College •Ortho R group strongly N N London (1993-2012) then Emeritus Professor favors ipso substitution • Visiting professor at Auckland University, Paris-Sud University •Meta favors [1,6] addition and Bordeaux University, Merck-Frosset Lecturer in Canada (1994) •Para has much less of • Fellow of the Royal Society of Edinburgh (2007) an effect • Recipient of Royal Society of Chemistry's Corday-Morgan medal, the Bader award, the RSC •Yields vary widely [1,6] Direct Substiution Tilden Medals and Lectureships (1998-99), the Silver Medal of the ICSN depending on substitution • Editor of Tetrahedron Reports • Co-authored 72 papers with Barton including the radical decarboxylation, radical Can also be used to form hetero–biaryls: deoxygenation, functionalization of saturated hydrocarbons with the GIF system and Me Organobismuth chemistry R1 R1 R1 R1 R1 NH N S S R1: Anomeric Carbohydrate Difluormethylene Derivatives N N N O 87% 69% 38% 29% 64% 19% incorporation AIBN CF2 Glycoside Derivatives 33% [1,6] addition 13% incorporation AIBN made in 1 step from sugar lactones para to NHMe on R1 para to NHMe on R1 OP OP OP OP RX, O F F F O F O O nBu SnH, Also investigated [1,6] vs [1,7] addition R %A %B SPh PhSH 3 R AIBN OR AIBN R F F F F O 4–CH 10 0 O S-centered O O C-centered O O OH 3 O radical O O O O S R radical O R S 2,4,6–CH3 0 36 Only 1 isomer O majority products give only 1 isomer I O 79-92% X H , 14–40% if R nucleophilic radical 2-CO2Me 0 90 Can be further reduced 2 B Pd/C EtO P 27–51% if electrophilic radical A EtO SePh Tetrahedron. 2015, 71, 6701 nBu3SnH OP O AIBN Formation other Heterocycles O S O O F OP O O H O S O F X nBu SnH F Poorer stereoselectivity 1 3 O R R1 O P(OEt)2 compared to other methods, AIBN Mechanism? F O substrate dependent High stereoselectivity O when X=O: 14–73% X= O or S when X=S: 0-94% 78-98% R2 R2 Originally were trying to make substituted styrene derivatives Heterocycles. 1997, 46, 523 Tetrahedron: Asymmetry, 1994, 5, 2269 Synlett. 1989, 68 Tetrahedron. 1997, 53, 15085 J. Chem. Soc., Chem. Commun., 1989, 1437 Baran Group Meeting Lisa M. Barton The Barton Family Tree 3/11/17

Organozinc Carbenoid Chemistry TMS enol ether did NOT give product, Also: Paul De Mayo O O Zn, TMSCl • B.Sc. from University College of the Southwest of England in Zn, TMSCl + Exeter (1944) • M.Sc. from Birkbeck College while working part-time with W. Rigby and F.V. Flynn (1952) Proposed Mechanism: • Ph.D. from Birkbeck College under Sir. Derek Barton (1954) • Lecturer at University of Glasgow and Imperial College while O Me3Si SiMe3 OSiMe3 O Cl ZnCl moving with Barton (1955-57) +e (Zn) +e (Zn) – (Me Si) O • Post doc with Robert B. Woodward at Harvard (1958-59) TMSCl TMSCl 3 2 • Professor than Director of the Photochemistry Unit at the University of Western Ontario until his death (1959-94) • Elected to the Royal Society of Canada (1971) and Fellow of the Reaction is substrate dependent Royal Society of London (1975) O O O O • Recipient of Merck, Sharp, and Dohme Lecture Award of the Zn, TMSCl Zn, TMSCl Chemical Institute of Canada (1966), E.W.R. Steacie Award in –30ºC –30ºC Photochemistry (1985), E.W.R. Steacie Award in Chemistry (1992) • 17 authorships with Barton including the elucidation of natural product structures and photochemical tranfomrations of these natural products De Mayo Cycloaddition •Control experiments showed only when used trans stilbene J. Chem. Soc., Chem. epoxide, not when benzpinacol or silyated benzpinacol used, Commun., 1973, 935 O Me O did McMurry type coupling occur J. Chem. Soc., Chem. •The use of 1,2-bis(chloromethylsilyl)ethane improves effeciency Commun., 1986, 1803 hν retro-aldol O + Me λ> 300nm Cyclopropanation HO O O Me O Types of substrates used: R2 O Proc. Che. Soc. 1962, 119 3 5 R1 R2 R1 • later expanded to wide range of alkenes and enones R R slow addition Can. J. Chem. 1963, 41, 440 R3 H • reacts through the triplet species which has very short lifetime Zn Ph R4 R6 Cl R4 Si R5 Surface Photochemistry Si R6 Cl O Photo-Fries Rearrangement of esters and amides (MeO)3CH O NH2 • For substituted aromatic aldehydes: Ph NH2 electron rich gave better yields and O NH2 O HN hν •Coversions Lower increase endo selectivity O + + than in solution but • stereochemistry of alkene preserved MeO NH NH λ> 300nm overall yields higher • E/Z stereochemistry enal lost MeO • cis selective preference for aromatic EtO OEt Ph O aldehydes, more planar enones no (formed in situ) On Silica: 30% 46% 9% preference and stereochemistry enone In Solution: 24% 28% 15% large effect on outcome Can. J. Chem. 1984, 62, 1275 • Different chiral N-diethoxymethyl amides Can also be rendered intramolecular: can select for either cis or trans Cis–Trans Isomerization: Dimerization N-Vinylcarbazole: H Me Me CdS powder CdS powder Me R R Cl hν hν Si N Si Me λ> 300nm λ> 430nm R N NR OHC Cl H R R 2 2 Me Me racemic Zn Me •In both cases oxygen significantly improves yield and rate of reactions Me Me Me Me Me Not Observed Not discussed: Photochemistry of thiocarbonyl compounds

J. Chem. Soc., Chem. Commun., 1992, 1582 Angew. Chem. Int. Ed., 2013, 52 J. of Physical. Chem. 1985, 89, 5815 Tetrahedron. 1986, 22, 6284 Chem. Commun., 1998, 2191 Tett. Lett. 1995 36, 1121 Eur. J. Org. Chem., 2009, 1532 Baran Group Meeting Lisa M. Barton The Barton Family Tree 3/11/17 .

David Crich Selenol Mediated Radical Chain Reactions • B.Sc. from the University of Surrey (1981) • PhSeSePh useful reagent for generating phenyl selenide as can be reduced in situ by • Ph.D (1981-84) then post doc (1984-85)at the Institut de Chimie des Bu3SnH Substances Naturelles under Sir Derek Barton and Pierre Potier • Prevents slow to moderate rearrangements of alkyl radical • Lectureship in Christopher Ingold Laboratories of University College H London (1985-90) O O O O Bu3SnH O O • Distinguished Professor Liberal Arts and Sciences of Organic AIBN + Chemistry at the University of Illinois at Chicago (1990-2007) • Schaap Professor of Chemistry at Wayne State University (2007-09, Br H 2011-present) • Director of ICSN (2009-11) without (PhSe)2: quantitative 0% with 10% (PhSe) : 82% 18% • Franco-British prize of the Academie des Sciences (1989), Corday 2 JOC 1995, 60, 84 Morgan medal (1990), RSC Tate and Lyle Carbohydrate Chemistry prize (1994), A. P. Sloan Foundation Fellowship (1994), ACS • Promotes chain reactions where Bu SnH/AIBN inefficient Carbohydrate Division Wolfram Award (2008), and ACS A. C. Cope 3 O Scholar and European Carbohydrate Society Emil Fischer Award (2011) Ph Ph • Curently Editor-in-chief of e-EROS Bu3SnH Note: Also required O Ph 40 mol% AIBN • Over 17 authorships with Barton including thiohydroxamic ester radical chemistry, and AIBN + deoxygenation of alcohols without (PhSe)2 to go to completion Br Carbohydrate Chemistry without (PhSe)2: 19% 3% Also 31% dimerized Reagents for the activation of thioglycosides with 10% (PhSe)2: 84% 0% OR OR JOC 1997, 62, 8624 • Catalyzes the addition aryl halides to arenes OR HO Promoter OR R'O O RO O O R'O OR' R'O RO O OR' RO R'O RO Bu SnH OR' O OR' 3 SEt I 15 mol% + + S AIBN •PhSOTf: OTf N O N N O N O O

– formed in situ from AgOTF and PhSCl without (PhSe)2: <5% 12% 23% – works at –78ºC, is high yielding, gives moderate to high β:α ratios with 10% (PhSe)2: 43% 22% 22% – active enough to form extremely hindered bonds with 3º OH JOC 1998, 63, 2765 – no need to oxidize to sulfoxide to activate JACS. 1998, 120, 435 O Fluorous Reagents •BPS: S N • Alternative to DMSO that can be easily recovered and reoxidized with H2O2 for Swern: O "Linkers consisting of only one S methylene group were found wanting – white, crystallline solid that is shelf-stable C4F9 – works just as well as PhSOTf at –60ºC, giving stoichiometric yields on the facile elimitation of HF from the • Protocol almost identical to Swern except at –30ºC sulfoxide" – protocol requires TTBP and Tf2O to form active tosylated reagent JACS. 2001, 123, 9015 • Gives yields 77-94% • 84-90% of reagent recovered (using FC 72 in a Tetrahedron. 2002, 58, 3865 •p–NO2PhSCl/AgOTf: continuous extractor O2N S OTf – commercially avaialbe • Alternative to (PhSe) : analogs with longer CF3 chains Carbohydrate Research 2 increasingly insoluable; tradeoff only – slightly lower β:α ratios than other two reagents C6F13 Se – TTBP occassionally as an additive to form active reagent 2008, 343, 1858 52% fluorine content decreases 2 efficiency fluorous extraction Tetrahedron. 1999, 55, 14261

Not covered: Mechanistic studies of glycosylation; Influence of neighboring groups in glycosylation development of asymetric glycosylation reactions Baran Group Meeting Lisa M. Barton The Barton Family Tree 3/11/17 Anthony G.M. Barrett Allyboration • B.Sc. and Ph.D at Imperial College under Sir Derek Barton (1975) Bidirectional 1)2x RCHO • Lecturer then Senior lecturer in organic chemistry at Imperial 1) n-BuLi, TMEDA; 2) H O (1975-83) filtration B B 2 2 • Professor at Northwestern University (1983-90) then at Colorado 35-45% State University (1990-93) 2) (+)-Ipc2BCl • Glaxo Professor of Organic Chemistry, Director of the Wolfson 2 2 Centre for Organic Chemistry in Medical Science, and Head of the OH OH OH OH Organic Section at Imperial (1993-present); Sir Derek Barton + Professor of Synthetic Chemistry (1999) • Fellow of the Royal Society (1999) and Academy of Medical R R R R Sciences (2003) • Hofmann Prize (1972), Royal Society of Arts Silver Medal (1973), • Gives moderate yields with good dr ( > 91:9) and excellent ee (>95%) Imperial College Armstrong Medal (1981), ACS Arthur C. Cope • Homochiral aldehydes give single isomer Scholar Awar (1986), Royal Society of Chemistry Award in Natural • (–)-Ipc2BCl can also be used to give opposite absolute stereochemistry Products Chemistry (2001) • preformed several experiments to see if intermediate could be used to make asymmetrical • About 24 autorships with Barton including the synthesis of dihydroxybenzoate derivatives, diols but typically 2nd allylboration proceeds faster so very low yielding synthesizing olefins from diols, and dissolving metal reductions of carboxylic esters • Used in synthesizing spiroketals present in moteifs of natural products:

1) n-BuLi, TMEDA; OH OH 1)O3; Me2S O 2) (+)-Ipc2BCl 2)DOWEX-H+ HO Lanthanide Catalysts 3) O THPO OTHP MeOH O Acetylation of alcohols with Acetic Acid THPO H HO 33% from 5 mol% Sc(OTf) 4) H2O2 ROH + AcOH 3 ROAc + H2O aldehyde JOC. 2000, 65, 375 • typically gives complete conversion (where as highest uncatalyzed 38%) • catalysts can be recyced • more atom economical Vicinal Diols 1) BuLi, TMEDA CHO • works for 1º, 2º, and 3º alcohols 2) B SiMe (Ni-Pr ) • Yb(OTf)3 works just as well, other triflates work but less efficient (Sc, La, Pr, Eu) BOMe 2 2 O NBoc Chem. Commun. 1997, 351 SiMe2(Ni-Pr2) Aromatic Nitration 2 2 10 mol% Yb(OTf) HNO + Aromatic 3 Ar-NO + H O BF3•Et2O 3 reflux 2 2 OH H SiMe2(Ni-Pr2) • Yb(OTf)3 and Sc(OTf)3 both give comparable yields with relatively electron deficient aromatics H2O2 B O (75–>95% except for Nitrobenzene which failed to react) KF, KHCO3 O NBoc • cataysts can be recycled 57% • no dinitrated products observed, about 1:1 para:ortho substitution NBoc OH 2 O Chem. Commun. 1997, 613

Gives good yields and excelent diastereoselectivity •Hf(OTf)3 and Zr(OTf)3 give complete conversion of o-nitrotoluene with same cat. loading as Yb Tett. Lett. 1998, 39, 1641 JOC. 1991, 56, 5243 Not covered: Heavier Group 2 Metal Catalysis Baran Group Meeting Lisa M. Barton The Barton Family Tree 3/11/17

Benzynes BuLi –78ºC to 0ºC; Gerhard Quinkert OMe OMe OMe R2 OMe R2 F O • Ph.D. from the Technical University of Braunschweig, Germany under H.H. Inhoffen (1955) F O HCl F • Post doc with Sir Derek Barton (1957-59) R F • Privatdozent (1961), Associate Professor (1963), and then Full 45–80% OMe Professsor (1967-70) at Braunschweig OMe OMe OMe OH • Professor Goethe University, Frankfurt am Main, Germany (1970-95) •low regioselectivities in boh cycloaddition and rearomatization JOC, 2005, 70, 3526 • Involved in the founding of Tetrahedron and Tetrahedron Letters • Elected to the National Academy of Sciences Leopoldina (1988) and Academia Europaea (1989) ent-Clavilactone B • Recipient of the Emil Fischer Medal, the Windaus Medal, and 1)t-BuPh2SiCl the Inhoffen Medal imidazole Mg, 4-bromo- O EtO2C • 1 paper and 2 patents with Barton including the synthesis of 96% 1-butene; dimethylcrocetin and the light induced opening of cyclohexadienones 2) n-BuLi; CuBr•SMe2 97% OH EtOCOCl OTBDPS O 99% Total Synthesis O O O R OH O 1)Ti(Oi-Pr)4, Me OH OH L-(+)-DET O O t-BuOOH DiBAl-H H H H A 93%, 97% ee 96% EtO2C Me O OH H H 2) (COCl)2, OH H H H O OTBDPS DMSO, Et3N OTBDPS OTBDPS HO O Estrone (-) Norgestrel (A) and (+) - aspicilin OMe Through both an (1) Norethindrone (B) Helv. Chim. Acta OMe OMe intramolecular n-BuLi; 1988, 71, 1719 F photochemically promoted A: R: Et A MgCl O + Isomer and an intermolecular chiral B: R: Me 65% * LA promoted Diels-Alder Helv. Chim.Acta 1985, MgCl Reactions 68, 1054 OMe OMe OH OMe OTBDPS Helv. Chim.Acta 1995, 78, 1345 2:1 in favor undesired Ph O 1) R–CH(CO CH ) , 1) TBAF 1) TBAF 2 3 2 B H O O CH OH, O O N 87% 86% O 3 H O AlMe O Na/CH OH, 60ºC then n 2)TEMPO 2)TPAP O 3 R H NMO O 130ºC Ph PhI(OAc) 3-n 2 74% O 2) CH OH, H O rt; 80% 3 2 O O H reflux; H 1) Grubb's II conc HCl; O OMe MeO tetrafluoro- (+)-Confertin NaH2PO4•H2O benzoquinone 1st asymmetric Methyl Jasmonate synthesis of 1st asymmetric synthesis of 0.03M Toluene O Lewis Acid B epi–Isomer O 80ºC Angew. Chem. Int. Angew. Chem. Int. Ed. Both use sequence to access 80% O O 65% Ed. Engl. 1987, 26, 61 Engl. 1982, 21, 856 enantiopure building blocks O 2) CAN, 74% OMe O Mechanism? O JACS 2006, 128, 14042 Baran Group Meeting Lisa M. Barton The Barton Family Tree 3/11/17 Robert Vyent Stick • B.Sc. and Ph.D from the University of Queensland under Fracis N. Lahey (1970) • Post doc with Ramond Lemieux at the University of Alberta (1970-1972) and Sir Derek Barton at the Imperial College of London (1973-1975) • Professor at the University of Western Australia (1975-08) • Recipient of the Doctor of Science award from the University of Queensland (2003) • Published two textbooks on carbohydrate chemistry •3 papers with Barton on the reactions of thiocarbonyl substrates with electrophiles and the synthesis of enamines from oximes Imidazole-1-sulfonyl Azide•HCl

•Inexpensive, shelf-stable, efficient alternative to TfN3 •Reacts with variety of amines with high yields (66-92%) and good functional group tolerance

O "Vigorous grinding and prolonged N N3 S N •HCl heating at 80ºC failed to invoke any explosive reaction" O Org. Lett. 2007, 9, 3797

VO(salen) as a catalyst to form Glycals O OAc OAc N N Zn, AcOH V O O AcO ACN AcO AcO O O VO(salen) AcO AcO Br 92% 1hour Aust. J. Chem. 2002, 55, 83

Carbohydrate Chemistry •Majority of carreer on methodology development for and total synthesis of carbohydrates •Includes the total synthesis of arsenosugars and glycosidase inhibitors •Used glycosynthase enzymes to synthesize inhibitors to same enzymes

O OH OH O O As OAc HO OH HO NH O O HO OH AcO O AcO Isofagomine (R)-2',3'-Dihydroxypropyl 5-Deoxy- Aust. J. Chem. OAc 5-dimethylarsinyl-β-D-riboside Optically pure inhibitors 2007, 60, 211 Aust. J. Chem. 1987, 40, 1901 Aust. J. Chem. 1990, 43, 665