- Email: [email protected]
Graphical abstracts
Tetrahedron: Agmmetry 1993,4,757
Total Synthesis of (-)-Oudemansin X Based on Enzymatic Resolution Using Immobilized Lipase. Hioyuki Akita*, Isao Umezawa Ma&o Nozawa and Shinji Nagumo, Schoolof Pharmaceutical Science,TohoUniversity, 2-2-l Miyama,Funabashi,Chiba, 274, Japan (-)-Oudemansin X (1) was synthesizedbasedon enzymaticresolutionof (f)-13015 using immobilized lipase. r
4
acetate (~)_5 iscQrqmnyl immcbilired liiase OH
on
(9S,l OS)_5 27% (97%@3)
Me0
OH OAc
COOYe
(-)-OudemanainX (1)
(9R.l OR)-6 66% (4%W3)
Tetrahedron: Asymmetry 1993,4, 761 ENZYMATIC RESOLUTION OF HINDERED SECONDARY ALCOHOLS: EFFICIENT ACCESS TO A NEW SIMPLIFIED CHIRAL AUXILIARY L.R.Randrianasoio-Rakotozafya, R.Azerad *a,F.Dumasb,
D.Potinb,
J.d’Angelo*b
et Biochimie Phanmxologiques et Toxxologiques, Universite R.Eexartes, 45 rue des Saints-Peres,75270 pari! Cedex06, France.b) Laboratoire & Chimie Orgauique,Faculte de Pharmacie,5 rue J-B Clement, 922% Ch?uenay-Malabfy Cedex,Fmce a) Laboratoire de Chiie
2,2_Diphenylcyclopentanol, an efficient chiral auxiliary, as well as related hindered secondary alcohols, were resolved by enantioselective hydrolysis of their acetate esters with pig liver acetone powder or horse liver acetone powder.
STUDIES
&;h
%F’h
+Ph
Ph
ON THE ENZYMATIC RESOLUTION OF CHIRAL TRICARBONYL
Tetrahedron: Asynmetry 1993,4,767
(BENZALUEHTDE OXl?.fE)CHROMIUM COMPLEXES
C. Baldoli ‘: S. Maiorana., G. Carrea b, S. Riva b ‘)CNR- CenIm Studio Sinksi Stereochiiu bkNR-,stiNto
di Cbmica deg,i &“o”i.
Sistani Mihno.
X
Orgmiei,
Dip,Chiiica
Orgmix
e Indus!xiale.
Univmitd
X
X
Tetrahedron: Asymmetry I!M3,4,773
CATALYSIS IN ORGANIC SOLVENTS. IN SEARCH OF PRACMCAL DERIVATIZING AGENTS FOR THE KINETIC RESOLUTION OF ALCOHOLS. H. S. Bevimkatil md R. V. Newadkar LIPASE
Alchmdc Rescwch Cenwc. ICIIn&
di Mila,
mA,-Y
Limited. Thaw-BelqnwRoad~ Than&W 601, India.
2-Phenyloxezolin-5+oo(2) acts LPa derivatizhqagent in the lipe catalyzedkineticresolution of N-ethoxycarbooyl-2-amino-lbotanol(1)in organicsolvents.
si (R.S)-1
+
Nq”
E==, -
FCOOEt AOH
Ph 2
NHCOOEt +
&O)+H’Ph 0
(0-l
ix
W-3
1
Tetrahedron: Asynmetty 1993,4,777
EFFECTS OF CHWICAL WODIFICATIONON STENEOSNLECTIVITY OF Pseudoamas CepacfaLIPASE. D. Bianchi”, a)Istituto
E. Battistela, G. Donegani,
b)Nagyar
Tudotinyos
A. Bosatti’,
P. Cesti
ENICHEM,Via Pauser
Akadeaia,
and 2. FekBteb
4 28100 Novara ITALY.
Veszpr&m 8201 ?lUNGARY.
Two chemically modified forms of lipase from P. Cepacfa were prepared by acylation of the amino groups of the proteln. The catalytic activity, the enantioselectivity and the thermal stability of the modified enzyme forms were compared with those of
the native
form in the hydralysis
Enzymatic
Resolution
of chiral
esters.
I Tetrahedron:Asymmetry 1993,4,783
of 3-Substituted-4-oxoesters
L. Blauco,* G. Rousseau,* J.-P. Bamier, E. GuibB-Jampel Laboratoire des Carbocycles, ICMO, Bk. 420, Universitt de Paris-Sud, 91405 Orsay (FRANCE)
RZ COOR
h +
;;o;pH ~
RI,&-
0
0
+R+mH 0
Tetrahedron: Asymmetry 1993,4,793
ENZYME-CATALYZED DESY METRIZATION OF mew-SKIPPED BUILDING BLOCKS POLYOLS TO USEFUL CHI icia Viggiani Dipsrtimento di Chimica, Carlo Bonini*, Rocco Racioppi, Universitadclla Basilica& Via N.P #ro 85.85100 Potcnza, Italy. Giuliana Righi, Len&o Russi Centm C.N.R. Per lo Studio &lla Chimica de&z.Sostanze N~turali, c/o Dipartimento di Chiiica,Universiti “La Sapienza”,P.le A.Moro 5,00185 Roma.
Thebiocatalytic dqmmetrization of pclyfunctionslizeddials in a meso form was studied.PFL was found to afford, PUrc enantiomer with opposite absolute configuration. The obtained chiral building block has been utilized for useful synthetic 0unsformations. 3R,5s or 3S,5R
Enzymatic Hydrolysis of Mesdqyc4obutene
1 Tetrahedron:Asymmetry 1993,4,807
Esters.
Ian Harvey and David H.G. Cdopt. Departmentof Chemistry, Unitwsity of Warwick, Coventry,CV4 7AL. Asymmetisation of dðyl mesu-3-cyclobutene I,2dicarboxylatcand ((lRM)-4_hyhxyn=thyl-2-cyclobutenyl)mcthyl
x
Tetrahedron: Asynmmy 1993,4,8 13 Kinetic Resolution Strategies II: Enhanced Enantiomeric Excesses and Yields for the Faster Reacting Enantiotner in Lipase Mediated KinetiC Resolutions S.M. Brown, S.G. Davies and J.kA. de Sousa The Dyson Pert-ins Laboratery, South Parks Road, Oxford OX1 3QY, UK.
48%peld
17%yield 37%overalyield
fR)-3
Tetrahedron: Aspmetty LIPASECATALYZEDRESOLUTIONOF RACEMIC 2.ALKYLSUBSTITUTED14LKANOLS StefanBarthandFranzEffenbergef, InstitutfiirGrganischeChemie,Universit% Stuttgart,Germany duty
pure(R)-2-~l-i-~~ot~
wereobtainedvia ~~~~~~
of twoccmlietiagsties.
1993,4,823
of racemicsubstra~ with vinyl
aeon
By twofoldester&&en also the (~-2-~1-1-~0~
acetate accordingto the them’y
werereceivedin highopticalpurity. R
y‘ R’
GH+@oAc
Lipase b WPZ
R-OH -, R
oAc + CH&HO
+R r
R’
Tetrahedron: Asymmetry 1993,4,835 Stereodivergent Synthesis of Fluorinated Thereonine Derivatives in High Optical Purity Makoto SHIh%IZU,Tetsuya YOKOTA, Kouichi ~J~ORI, and Tamotsu ~JISAWA* Department of Chemistry for Materials, Mie University, Tsu, Mie 514, Japan
AcO
R+oEt
0
N-Ok!%
l)Lipase ~ 2) Reduction
HO
0
HO
b
R’kKOEt+ R/\/COEt
liH2
NH2
R = CHzF, CHF2, CF3,CH2Cl
Tetrahedron: Asymmetry 1993,4,839 CONVENIENT PRACTICALRESOLUTIONOF RACEMIC ALKYL-ARYLALCOHOLSVIA ENZYMATICACYIATIDN WITH SUCUNK: ~YDRtDE IN ORGANICSOLVENTS A& L. ~u~~,* DovBnnnerandAvivBoltanski
Department of Ckemisay,Technion- lsrselinstituteof Technalogy,Haifa32W0,Lstael
Enfmtiomericall we alkyl-arylsecondaryalcohols were convenientlyobt$ned on a kilogrammeseaf3 e y enzymaticacylationwith succ~n~canhydridein orgamcsolvents.
xi
t
1
~~~~o~: BEGIO- AND RNANTIOS ECTIVR ESTERIFICATIONS OF ~LYOXYGENATED CATALYZED BY LIPASES !? O~~DS
cuff
1993,4,845
A~~~
1993,4,875
Derivatives of both enantiomem of propane-1,ZZtriol (A) and cis-2-aryl-4-hydroxymethyl- l&dioxane (B) have been prepared throughlipase catalyzed tramekterifications.
Tefra~~un:
LIPASEAPRON
~lffS-3.7-D~RO~CY~~ ~~~~~ INORGANXCANXIAQUEOUSMEDIA Smu 1. Es* D. Todd Wtlitaker~ 8nd 1 R. fohnsm? u: Uti~msity,DeMt MI 48202 WA ~~~~ of Chemisry, Wayne St6”
~Qo~+A~QQ%cg.M
The
nnestr-diol and conesponding diacetates of cycloheptene deriwives were subjected to enzymatic asymmtizations using lipase from Pseudomonas cepacia in organic and aqueous media.
of Chernisq,
801 SIdmoke H3A 2K6 CANADA
0
St, W.. Mom&l, Qu5bcx
1r~s-2-Bromo-l-~yl~y~c~~~a from fwu&ww CcQveaedto cyclic allylic ak&ols.
w+m resolved with lipaae
*a&$*H
(CE ‘&, C7) C@pcti and
+
A
0qO)Pr **%
xii
0
“&-$oAc cl
-c
c+(&&
Asymmetric Synthesis of Both Enantiomers Acyloxy Methyl 3,3-Difluorolactate
Tetrahedron: Asymmetry 1993,4,889
of
Kouichi Murata and Tomoya Kitazume Department of Bioengineering, Tokyo Institute of Technology Nagntsuta,
Midori-ku,
Yokohama
227
Tetrahedron: Asymmetry 1993,4,893
A SIMPLE TOTAL SYNTHESIS OF NATURALLY OCCURRING HYDROXY-AMINO ACIDS BY RESOLUTION ENZYMATIC KINETIC
Yang Lu. Christine Miet, Nicole Kunesch*, and Jacques E. Poisson, J_abomtoirede Chimie des Substances p-h@z=zNdl-
PbamweutiqueJ, 922% Chitenay-Malabry CFiJXX,
FRANCE
Both optically pure enantiomers of GABOB and isoserine were obtained by enzymatic kinetic resolution of acetylated precursors in three or four steps with cyanohydrins as key intermediates.
Tetrahedron: Asymmetry 1993,4.903
Enzymatic Resolution of Aziridiie-Catboxylates. MariaBucciamlli,ArrlgoForni, Irene Moretti*,Fabio Prati and GiovanniTone Dipartimentodi Chin&a dellWaivenita’,via Campi, 183,41100,Mcdeaa, Italy.
N-acyl-aziridine-2-carboxylates and N-acyl-aziridine-2,3dicarboxylates have been resolved with good to excellent stereochemical purity by enzymatic hydrolysis catalyzed by lipase from Candida cyhdracea. COGCH, (-)-(%3R)
6)-W H r
R = CH3; n.C3H7
COOCHB
COR
Tetrahedron: Asymmetry 1993,4,907
ENZYME REACTIONS IN AFOLAR SOLVENT. 6. THE EFFECT OF DOUBLE BOND ISOMERISM ON THE RATE OF PPLOAT~Y~~DAOYLATI~N OF ALLYLIC ALCOHOLS Brian Morgan #* and Allan C. Oehlschlager Department of Chemistry, Simon Eraser University, BurnabyB.C.. CanadaVSA IS6
Pancreaticporcine lipase (PPL) preferentiallyesterifies the (E)- isomers of lo and 2’ allylic alchohols. R? %
OH
PPL R4
+
Triflouroethyi butyrate
Rl
...
x111
ENZYb5cATALyzED
C ACYLUION AND HYDROLYSISOF
QRUVATIVESzCQNTRIBUTlON Tetrahedron: Asymmetry 1993,4,911 TODJWELOPMENT OFMODFXS F$R REACITONS CATALYZED BYPORCINE LIVEREsFERASEANDPORCINE PkNCREWCUP/GE Koichixo Nacmura,* Ritsuko Fuw, Nobuo Takahasbi, Masayosbi Konisbi, Yoshiki HIrose, and Yosbito Tobe Department of Chemistry, Faculty of Engineering Science, Osaka University, Toyonaka, Osaka 560, Jqmj Lipase YS catalyzed acyiation of #be c&-dial 2 in cyclohexa~ gave the cismonogcttate f-)- 3 and PLE, PPL, &ase YS, and CCL catalyzed hydrolyses of the kdiacetate I gave also optically active 3. c&2,5-DISUBSTTWfRD
lipase YS,
PLE,
CCL
(-J&C in butfer solution A@
,
OAc
PPL
in buffer
w
SOh.#i&
Tetrahedron: Asymmetry X993,4,919 Separation of Stereoisomerik l.l’-Bis(a-hydroxyethyl)ferrocenes by Lipase-Mediated Acetyl+ion in Organic Solvent D. Lambusta, G. Nicolosi,*’ A. Patti and M. Piattelli Istituto CNR Studio Sostanee Naturali, Via de1 Santuario 110, 95028 Valverde CT, Italy H
CHa OH
FO
+ CUa=CH-OAc.
-
~
~~
~~
OH
4 ”
Ha
P~ez&monas
CHa
cepaciu lipas
CHa
in acetone allows the separation of (R,R)-, (S,S)- and (R&-isomers of I,1 ‘-bis(a-hydroxyethyl) i:errocene.
Tetrahedron: Asymmetry 1993,4,925 RESOLUTION OF DIOLS WIWH C -SYMMETRY BY LIPASE CATALYSED TRANSESTERIFICATION 3 , andTorbj6m Norin’ Huit AI&s h4atWn’. Niias OhmeG, Department of ~~~ andBio~~~~z ~~~t~~~~~* Royal Jnstitute of Technology,S-lF 44 Stcckholm,Sweden Theresolutionof dialswithCz-symtnetryby lipasecatalysedtramestetificatioc wasdemonstmted. Thedials wereobtainedin high vields with99% ee in mastcases.
Tetrahedron: Asymmetry 1993,4,93 1 SELECTIVE LIPASE-CATA YZED ACYLATION OF 4,6-0.BENZYLIDENE-D-GL COPYRANOSIDESTO SYNTHETICALLY USEFUL $STERS via L&i Panza,a Sara BrascaP S ‘o Rivab and Giovanni Russ@ 0 ~iflrytinrtno di cwcu &gmica c kdwtriak Venniaa,21 - 20133 Mikmo - ItalR. Is&to di Ckmicu &gli Orrnoni,ChWvia Maria Bianco, 9 -20131Milan0 - Iit+ Lipase-catalyzedregiosektive ztcylationofmethyl4,6-O-benqkiene-a- and P-D-gk.opyranosiQs is de&be& Ph
~iosee P _Ph Activated ester
xiv
1
Tetrahedron: Asymmetry1993,4.933
EnzymaticResolutionof Acylatesof Pm&al Phenolicl-A+ and l-ArylaUryl-l,2,3,4Jy~~~o~ls, whichpossessa GuaiacoltypeMoiety,by use of ImmobilizedLipasein mic Solvent OsamuHo&in~,*~RukaTaaahashi,aMitauhimOkxia,a HiroyukiAkitap andTake& OishiC Facultyof Pharm.Sciences,ScienceUniversityof Tokyo, Shinjuku-ku,Tokyo 16za Facultyof Pharm.Sciences, TohoUniversity,Miyama,Funabashi-shi, Chiba274;b MeijiCollegeof Pharmacy,Setagaya-ku,Tokyo154,cJapan Kineticresolution using lipase immobihed
S-. 6- or 7-OA.z
with c&e
U-854 (2%%.a$ GmR)
8.76% (5.72%ez) Pm.9 a: lip&?.organicsolvent
yy$&y (n=O. 1,2)
in organic solvent was carried aa.
Tetrahedron: Asynmetry 1993,4.943
Immobiization of Substrates in Ewyme-Catalyzed Hydrolysis
Chi-Hsin R. King and Alexey L. Margolin*, Marion Merrell Dow Research Institute, 2110 E.Galbraith Rd. ,Cincinnati, OH 45215 USA A new technique - immobilzation of substrates on solid supports - was applied to the synthesis of a new potent optically pure serotonin receptor antagonist (R-l).
Tetrahedron: Asymmetry1993,4,947 An Enzyme-Based Synthesisof(S)_(+3-Methyl-2[(phenylsuIfaay?am?thyllbutyl Phenyl Sulftie and the Stereocbermcrl Course of its Alkylation RouanGuevel and Leo A. Paqueue* EvansChemicalLdnmtories, The OhioStateUniversity, Columbus, Ohio 43210 Lipase P-30 hydrolysis of 9 finds the (,Y)-
oLa
enantiomerto be lessreactive. Conversion of this material (>95% e.e.) to (-)-11 was
followed by highly diastereoselective akyk tion to give, for example, (-)-W.
H Qw
w?m
m
AJ H’
-
IPll (g-11
(-)-O
J&? m
-
Ii
km (g-13
I
Dimtare andEaatio&lectin Bstuifii
Lipapeflom-fl-ns. Ki$alS.BisbtandViiS.Parma+
Enantband-vcacety~on of racemicplusmcs&&ne2,3-diol.
of Butatw23diol Catdysedby tk
Tetrahedron:Asymmetry 1993,4,957
1
Enzyme catalysed resolution of aminophosphoaic acids - I .
Tetrahedron:Asymmetry 1993,4,959
Setin and Isoserin analoguea
A. Hais@, C. R&ilk@. R. Douilb% N. Goaloa? G. Htt8ebb andF. Levaya@ ~LabpntoiradcRMNetde~v~~~~4722~&l~~~,F~2N~~~~~) IashIatflir AaOr8aaischa cbcmia und.%ktamhe&, I-LH&e-KJaivasittt,IJaiv~it&ss@c1,Dm
Cd-&fit)
K,IU A
1 2
0
R
0
a4
R’ viilwtalc PI tipas
R=-P(O)(OMe~.R’=H 34%1eonversion R=H.r=-P(o)(oE& -
MISSBLDGRJ1(GERMANY)
Roduclobtained
R
C&0G
I”Y I HOCOCH, No eaaatios&ctivity
84mGgumtianonly (cc 0 1c0%)
Enzymatic Resolution of Bulanoic Esters of 1-Phenylmethyl 1-[2-Phenylethyl] Ethers of !3-Chloro-1 ,P-Propanediol
and
Tetrahedron:Asymmetry 1993,4,961
Vaasilia Par&, Viggo Waagenl, Thor Al& and Thorleif Anthonsen’ 1, Department of Chemistry, Thtj University of Trondheim, N-7055 Dragvoll, Norway 2, Borregaard Fine Chemicals, P.0. Box 256, N-1701 Sarpsborg, Norway
I
rat
R = CH,Ph,
E=15 R = CH,CH,Ph, E=25
s
f?
--
ENZYME- CATALYSED ESTEdlFlCATlON OF Tetrahedron:Asymmetry 1993,4,969 (*) - TRANS - CYCLOHEXANE : 1.2 - DIMETHANOL. Stanley M. Roberts’, Vemnique 0. R. Steukers’ and Philip L. Taylo? ‘Departmentof Chemistry, University of Exeter, Exeter EX4 4QD, Devon, UK, *Research Department, ICI Paints Division, Wexham Road, Slough SL2 5DS, UK A Lipozymecatalysed esteriticatioa process produced diester (A) in ca 83% ee.
Tetrahedron:Asymmetry 1993,4,973 C BLOCKS USING PSEUDOMONAS FLUORESCENS SYNTHESIS OF CHIRAL BUIL C HYDROLYSIS OF hfES0 DIACETATES LIPASE CATALYZED ASYMM Zhuo-FengXie, Him&iSuemuneI? 4 KiyoshiS&a?’
Facultyof Pharmaceutical Sciences;gyushuUniversity,Fukuoka812,Jspn
Aed)(2oAe Ii Me
-pFL
IHeAc
Ac&AF
(>99% e.e., 33%)
“C&OAc
(96%e.e., 79%)
xvi
Highly Asymmetric Enzymatic Hydrolysisand Transest&icatioa of mtso-Bis(acetoxymetbyl)and Bis(hydroxymctbyl)cyclopentane i)criv&es: An Knsigbt into the active Site Medel of Rkiropns MarahsmTan&a,MikiYoshioha,andKiyeshiSahai* Fady
ofPhammceukal
I D&mar
Sciences. Kywhu Univertiry.Fukuoka
Tetrahedron: Asymmetry 1993,4,98 1
Lipase
812,Japan
RDL- or PFL-catAysal
hydrolysisof mw-dimetate a&&d the chhaimoneawate (>99%ee).whichwasccovened into the (-)&steromycin. 4Hs
>99%ce (-)-Aristeromy
RDL A= Ao (0rPPL)
HO OH
Tetrahedron: Asynmetry 1993,4,997 STUDIES ONTHE ENANTIOSELECTIVITYOF THE TRANSESTERIFICATION OF 2-METHYL1,4-BUTANEDIOL AND ITS DERIVATIVES CATALYZED BY Pseudomonusj7wrescen LIPASE IN ORGANIC SOLVENTS. P. Grisenti,P. Ferraboschi,S. Casati,E. Santaniello* Dipartimentodi Chimica e Biochiiica Medics, Universita’di Milano,50-1-20133,Milano,Italy The irreversible txansestetitkation catalyzed by Pseudomonasjluorescens lipase has been used for the resolution of racemic 2-methyl-1,4-butanediol la and its benzyl ethers 29 and Ja, the best ee having been obtained for 2a (z.9896).
“OJ-LHPh HOdO”ehCH20J-LOH Tetrahedron: Asymmetry 1993,4,1007
Factors affecting the lipnse catalyzed lransestwl5.
cationrescttonxat 3hydroxy estenrtn otgsnic selventa.Uwe Bomchewr, Nagoya Univwity, DcpLcP Focd Scienceand Technology,Furc-cbo,Chikuu-ku,Nagoya 464-01, Japo,
AndreaHerar,L.am Kreye,VclkorWend4 An&em Capewell,Inrt Teoh.Ckem.Callinrtx3,300O Hannover1, Germany,HamnutH. Meyer,Inst.Org. Chem.,SchneiderberglB, 3000 Hanacvw 1, Germany,‘TlmmasScheper’,Inat Bicchem.Abt. Biotecbnclogie,IJniveniQtMUnrter,Wilhelm-Klamm-Str. 2,440O Miinrter,Germany, F&kc% N. K&ii, Dept Chem.En&,NationalTechniul Univenily Athena, Zogra~cu Cdmpur,15700 Athena,Gmcce. Tbe enaatioselectiviiy of rmnr&wifica~Icn reactionawith 3-hydmxyeaten in several organicsclvenb couldbe influencedandchangedby rclvent,lipae and acylatingagent.Reactionswere alsc performedat controlledpH, water contentandw&r a&&y. Kineticstudieswere performedin the optimizedsystem resultingin sub&rateinhibitioncausedby PIIcxcss of vinylacetateandthe slow reacdngenantiomarof therxemic 3-hydrcxyester.
of
,uaR,
+,.Ao,,,,
“pm0
b
R
‘u,,
+
R”‘.OH
organic sohrsnt
Enzyme
Assisted
Synthesis
of
Enantiomerically
Pure
Tetrahedron: Asymetry 1993,4,1017
CLactones BernhardEaase and Ma&d P. Schneider’,FB 9 - BetgischeUnivetsit&CiH-Wuppcual,B-5603Wuppcrtal 1. Germany
xvii
Tetrahedron: Asymmeny 1993,4,1027
Lipase Catalyzed Formation of Lactones via Irreversible Intramolecular Acyltransfer MarioLobe.11 and ManfrcdP. Schnci&r*, FB 9 - BergischeUniversitit-GH-Wuprtal,
W-5600 Wuppertal 1,Gemmy
lipase from
C&13 Y
H ‘:
Pseu4kmona.s sp.
(CH2)10 ‘COOCH=QI, OH
(+)-3f
cdl13
&
moIecuhu sieves 4 A hexane 66’C, 24 h
0 cz
(R)-4f 32 % 0
1 I
1 Tetrahedron:Asynmetty 1993,4,1031
Pen G Acylase Catalyzed Resoltttion of Phenylacetate Esters of Secondary Alcohols. E. Baldarog, P. D’Arrigo, G. Pedrocchi-Fantoni, C.M. RoselI#, S. Servi A. Tagliani and M. Terreni. Dipartimento di Chimica, Politecnico di Milano, Italy, 8 Rccotdati, S.p.A. De.Bi.Milano, Italy, #Institute de Catalisis y Petrolquimica, Madrid, Spain. OH
Pen Gi acyiase Ph--?f”yR 0
1
-b
PbT”YR
+
R’
R’
Tetrahedron:Asymmetryl!B3,4,1035
Enzymaticresolutionsin 3-aniino-1.2~propane4liol series M.-A. Mbapp6and S. Sicsic Biocis-CNRS,Faculti de pha@acie,Chatenay-Malabry,922%, France. A-i_ OCOR H 2
A
-OH AcNH ?iH
+
ATOCOR OH
i: hydrolysiswithE30000,iixcylationwithbeefliveracetonepowder The re.solutionof 3-amino-1,2propane&iol derivativeshas been carriedout by way of enzymaticcatalyscd hydrolyses or acylations.
Tetrahedron: Asymmetry1993,4. 1041
Enzymatic Resolution of ;N-Dialkyl-3-hydroxy-4pentenamides, Unsuccessf r I in Resolution by the
Katsuki-SharDless
Asyhmetric
Epoxidation
Hiroki Takahata,* Y&mhiro c da, Yoshie-Ohkawa, and Takefumi Momose* Faculty of Pharmaceutical Scie? ces, Toyama Medical & Pharmaceutical University, Sugitani 2630, Toyama 930-01, Japan On OH immot$l/zed
R’R2N
fi
lipase
) 0 1
vinyl acetate pentane
R’R2N
fi
0 (W-1
...
xv111
.
+
.,2N4y (SW
1
EnantiocomplementaryPreparationof OpticallyPure 2-Trimethylsilylethynyl-2cyclopentenolby Homochiiion of RacemicPrecursors: A New Route to the Key Intermediateof 125~Dihydroxycholecalcif&andViiine SeiichiTakano,’ Mahito Suzuki,and Kunio Ogasawara PharmaceuticalInstitute,TohokuUniversity,Aobayama,Sendai 980,Japan
4 Mitsunobu
1
1Mitsunobu
R= --TM
reaction
Tetrahedron:Asynmwy 1993,4,1043
4
reaction
STEREOSELECTIVE HYDROLYSIS of SUBSTITUTEDCYcLoPJ?NTANE DIESTRRS with PIG LIVRR ESTEIUSE @LE).
Tetrahedron: Asymmetry 1993,4,1047
Peter Renold and Christoph Tamm Institut fti Organ&he Chemie der Universitit Basel, St. Johanns-Ring 19, CH-4056 Basel, Switzerland $+zIM@G~;~z;~
Compounds 2,3,4a, Sa, 6a and
7a were hydrolysed by PLE (e. e. values 6-73%).
R2 4a R’= 0H,R2=CH20H 6a R’ - CH20H, Rz = 3H
Terrahedron: Asymmetry 1993,4,105 1 10666 N. TorreyPines Rd., La Jolla, CA 92 037USA OH 0
Pseudomonas lipase
OH 0
OAc0
Lii-catalyzed
resolution of 3-hydroxwic acid and glycosylatioausing gluwsyl phosphite as reagent
Preparation of 6-Deoxy-6,6,6-trifluoro-D-mannose and n-Allose from Enzymatically Resolved 2-Butenolides
Tetrahedron: Asymmetry 1993,4,1059
TakashiYamazaki,*Kenji Mizutani,and TomoyaKitazumd Departmentof Bioengineering,TokyoInstitute of Technology,Nagatsuta,Midori-ku,Yokohama227, Japan
xix
Tetrahedron: Asymmetry1993,4,1063
NITRILE OXIDES IN MEDICINAL CHEMISTRY. 5. LIPASE PS-CATALYZED RESOLUTION OF A SET OF HETEROCYCLIC DERIVATIVES.
Giacomo Camea,’Paola L.iverani.Sergio Riva, fstituto di Cbimica degli Ormoni. C.N.R. -Via Mario Bianco.9 - 20131 MILANO (IMY) MarcoDe Amici. Carlo De Micheli, Marta Camielli. Dipartimentadi Science Farmaceudche,UniversiP di [email protected]=TE (Italy). Br
)-x I
lipase PS
OCOGH7
h”Ef&
N\O (*)
*
I>OH
+
(R)-(-): e&.=94%
k-&_$, (S>(+): e.e. >99%
Lipase from Pseudomonas cepacia (lipase PS) catalyzed the hydrolysis of a series of buyrates of primary alcohols carrying a A2-isoxazolineor an isoxaaolidin-3-onenucleus.
CHEMOENZYMATIC SYNTHESIS OF ACETYL (R)-(t)- AND (S)-(+CYCLOSERINE
Tetrahedron: Asymmetryl!B3,4,1073
Marco De Amr~. Carlo De Micheli.’ FraocescaCateni. Dipartimentodi Scienm Farmaceuciche. Universitsdi Trieste.34127 TRESTE (Italy). Glacomo Carma. Gianluca Ottolma. fsrimlodi Chimica degli Ormoni. C.N.R. - Via Mario Biaoco.9 - 20131 MdanOWyl. BzlO
OCOCsH,
~OGH7
N/ ‘? ‘0 (f)
lipase CV “E”;;
-“‘ouon
+ e.e. >99% (RI-(+)
Bdoj-J e.e. >9?w (Sk(-)
xx
The IWOenantiomers of acetyl cycloserine were prepared in e.e. >98% through Ihe hydrolysis of 3-benzyloxy-4-hydmxy-A*~jsoxazoline botyrate under the catalysis of lipase from chromebocrerium viscosum. The reaction spontaneously Sloppedat 50% conversion of the substrate,
Total Synthesis of (-)-Oudemansin X Based on Enzymatic Resolution Using Immobilized Lipase. Hioyuki Akita*, Isao Umezawa Ma&o Nozawa and Shinji Nagumo, Schoolof Pharmaceutical Science,TohoUniversity, 2-2-l Miyama,Funabashi,Chiba, 274, Japan (-)-Oudemansin X (1) was synthesizedbasedon enzymaticresolutionof (f)-13015 using immobilized lipase. r
4
acetate (~)_5 iscQrqmnyl immcbilired liiase OH
on
(9S,l OS)_5 27% (97%@3)
Me0
OH OAc
COOYe
(-)-OudemanainX (1)
(9R.l OR)-6 66% (4%W3)
Tetrahedron: Asymmetry 1993,4, 761 ENZYMATIC RESOLUTION OF HINDERED SECONDARY ALCOHOLS: EFFICIENT ACCESS TO A NEW SIMPLIFIED CHIRAL AUXILIARY L.R.Randrianasoio-Rakotozafya, R.Azerad *a,F.Dumasb,
D.Potinb,
J.d’Angelo*b
et Biochimie Phanmxologiques et Toxxologiques, Universite R.Eexartes, 45 rue des Saints-Peres,75270 pari! Cedex06, France.b) Laboratoire & Chimie Orgauique,Faculte de Pharmacie,5 rue J-B Clement, 922% Ch?uenay-Malabfy Cedex,Fmce a) Laboratoire de Chiie
2,2_Diphenylcyclopentanol, an efficient chiral auxiliary, as well as related hindered secondary alcohols, were resolved by enantioselective hydrolysis of their acetate esters with pig liver acetone powder or horse liver acetone powder.
STUDIES
&;h
%F’h
+Ph
Ph
ON THE ENZYMATIC RESOLUTION OF CHIRAL TRICARBONYL
Tetrahedron: Asynmetry 1993,4,767
(BENZALUEHTDE OXl?.fE)CHROMIUM COMPLEXES
C. Baldoli ‘: S. Maiorana., G. Carrea b, S. Riva b ‘)CNR- CenIm Studio Sinksi Stereochiiu bkNR-,stiNto
di Cbmica deg,i &“o”i.
Sistani Mihno.
X
Orgmiei,
Dip,Chiiica
Orgmix
e Indus!xiale.
Univmitd
X
X
Tetrahedron: Asymmetry I!M3,4,773
CATALYSIS IN ORGANIC SOLVENTS. IN SEARCH OF PRACMCAL DERIVATIZING AGENTS FOR THE KINETIC RESOLUTION OF ALCOHOLS. H. S. Bevimkatil md R. V. Newadkar LIPASE
Alchmdc Rescwch Cenwc. ICIIn&
di Mila,
mA,-Y
Limited. Thaw-BelqnwRoad~ Than&W 601, India.
2-Phenyloxezolin-5+oo(2) acts LPa derivatizhqagent in the lipe catalyzedkineticresolution of N-ethoxycarbooyl-2-amino-lbotanol(1)in organicsolvents.
si (R.S)-1
+
Nq”
E==, -
FCOOEt AOH
Ph 2
NHCOOEt +
&O)+H’Ph 0
(0-l
ix
W-3
1
Tetrahedron: Asynmetty 1993,4,777
EFFECTS OF CHWICAL WODIFICATIONON STENEOSNLECTIVITY OF Pseudoamas CepacfaLIPASE. D. Bianchi”, a)Istituto
E. Battistela, G. Donegani,
b)Nagyar
Tudotinyos
A. Bosatti’,
P. Cesti
ENICHEM,Via Pauser
Akadeaia,
and 2. FekBteb
4 28100 Novara ITALY.
Veszpr&m 8201 ?lUNGARY.
Two chemically modified forms of lipase from P. Cepacfa were prepared by acylation of the amino groups of the proteln. The catalytic activity, the enantioselectivity and the thermal stability of the modified enzyme forms were compared with those of
the native
form in the hydralysis
Enzymatic
Resolution
of chiral
esters.
I Tetrahedron:Asymmetry 1993,4,783
of 3-Substituted-4-oxoesters
L. Blauco,* G. Rousseau,* J.-P. Bamier, E. GuibB-Jampel Laboratoire des Carbocycles, ICMO, Bk. 420, Universitt de Paris-Sud, 91405 Orsay (FRANCE)
RZ COOR
h +
;;o;pH ~
RI,&-
0
0
+R+mH 0
Tetrahedron: Asymmetry 1993,4,793
ENZYME-CATALYZED DESY METRIZATION OF mew-SKIPPED BUILDING BLOCKS POLYOLS TO USEFUL CHI icia Viggiani Dipsrtimento di Chimica, Carlo Bonini*, Rocco Racioppi, Universitadclla Basilica& Via N.P #ro 85.85100 Potcnza, Italy. Giuliana Righi, Len&o Russi Centm C.N.R. Per lo Studio &lla Chimica de&z.Sostanze N~turali, c/o Dipartimento di Chiiica,Universiti “La Sapienza”,P.le A.Moro 5,00185 Roma.
Thebiocatalytic dqmmetrization of pclyfunctionslizeddials in a meso form was studied.PFL was found to afford, PUrc enantiomer with opposite absolute configuration. The obtained chiral building block has been utilized for useful synthetic 0unsformations. 3R,5s or 3S,5R
Enzymatic Hydrolysis of Mesdqyc4obutene
1 Tetrahedron:Asymmetry 1993,4,807
Esters.
Ian Harvey and David H.G. Cdopt. Departmentof Chemistry, Unitwsity of Warwick, Coventry,CV4 7AL. Asymmetisation of dðyl mesu-3-cyclobutene I,2dicarboxylatcand ((lRM)-4_hyhxyn=thyl-2-cyclobutenyl)mcthyl
x
Tetrahedron: Asynmmy 1993,4,8 13 Kinetic Resolution Strategies II: Enhanced Enantiomeric Excesses and Yields for the Faster Reacting Enantiotner in Lipase Mediated KinetiC Resolutions S.M. Brown, S.G. Davies and J.kA. de Sousa The Dyson Pert-ins Laboratery, South Parks Road, Oxford OX1 3QY, UK.
48%peld
17%yield 37%overalyield
fR)-3
Tetrahedron: Aspmetty LIPASECATALYZEDRESOLUTIONOF RACEMIC 2.ALKYLSUBSTITUTED14LKANOLS StefanBarthandFranzEffenbergef, InstitutfiirGrganischeChemie,Universit% Stuttgart,Germany duty
pure(R)-2-~l-i-~~ot~
wereobtainedvia ~~~~~~
of twoccmlietiagsties.
1993,4,823
of racemicsubstra~ with vinyl
aeon
By twofoldester&&en also the (~-2-~1-1-~0~
acetate accordingto the them’y
werereceivedin highopticalpurity. R
y‘ R’
GH+@oAc
Lipase b WPZ
R-OH -, R
oAc + CH&HO
+R r
R’
Tetrahedron: Asymmetry 1993,4,835 Stereodivergent Synthesis of Fluorinated Thereonine Derivatives in High Optical Purity Makoto SHIh%IZU,Tetsuya YOKOTA, Kouichi ~J~ORI, and Tamotsu ~JISAWA* Department of Chemistry for Materials, Mie University, Tsu, Mie 514, Japan
AcO
R+oEt
0
N-Ok!%
l)Lipase ~ 2) Reduction
HO
0
HO
b
R’kKOEt+ R/\/COEt
liH2
NH2
R = CHzF, CHF2, CF3,CH2Cl
Tetrahedron: Asymmetry 1993,4,839 CONVENIENT PRACTICALRESOLUTIONOF RACEMIC ALKYL-ARYLALCOHOLSVIA ENZYMATICACYIATIDN WITH SUCUNK: ~YDRtDE IN ORGANICSOLVENTS A& L. ~u~~,* DovBnnnerandAvivBoltanski
Department of Ckemisay,Technion- lsrselinstituteof Technalogy,Haifa32W0,Lstael
Enfmtiomericall we alkyl-arylsecondaryalcohols were convenientlyobt$ned on a kilogrammeseaf3 e y enzymaticacylationwith succ~n~canhydridein orgamcsolvents.
xi
t
1
~~~~o~: BEGIO- AND RNANTIOS ECTIVR ESTERIFICATIONS OF ~LYOXYGENATED CATALYZED BY LIPASES !? O~~DS
cuff
1993,4,845
A~~~
1993,4,875
Derivatives of both enantiomem of propane-1,ZZtriol (A) and cis-2-aryl-4-hydroxymethyl- l&dioxane (B) have been prepared throughlipase catalyzed tramekterifications.
Tefra~~un:
LIPASEAPRON
~lffS-3.7-D~RO~CY~~ ~~~~~ INORGANXCANXIAQUEOUSMEDIA Smu 1. Es* D. Todd Wtlitaker~ 8nd 1 R. fohnsm? u: Uti~msity,DeMt MI 48202 WA ~~~~ of Chemisry, Wayne St6”
~Qo~+A~QQ%cg.M
The
nnestr-diol and conesponding diacetates of cycloheptene deriwives were subjected to enzymatic asymmtizations using lipase from Pseudomonas cepacia in organic and aqueous media.
of Chernisq,
801 SIdmoke H3A 2K6 CANADA
0
St, W.. Mom&l, Qu5bcx
1r~s-2-Bromo-l-~yl~y~c~~~a from fwu&ww CcQveaedto cyclic allylic ak&ols.
w+m resolved with lipaae
*a&$*H
(CE ‘&, C7) C@pcti and
+
A
0qO)Pr **%
xii
0
“&-$oAc cl
-c
c+(&&
Asymmetric Synthesis of Both Enantiomers Acyloxy Methyl 3,3-Difluorolactate
Tetrahedron: Asymmetry 1993,4,889
of
Kouichi Murata and Tomoya Kitazume Department of Bioengineering, Tokyo Institute of Technology Nagntsuta,
Midori-ku,
Yokohama
227
Tetrahedron: Asymmetry 1993,4,893
A SIMPLE TOTAL SYNTHESIS OF NATURALLY OCCURRING HYDROXY-AMINO ACIDS BY RESOLUTION ENZYMATIC KINETIC
Yang Lu. Christine Miet, Nicole Kunesch*, and Jacques E. Poisson, J_abomtoirede Chimie des Substances p-h@z=zNdl-
PbamweutiqueJ, 922% Chitenay-Malabry CFiJXX,
FRANCE
Both optically pure enantiomers of GABOB and isoserine were obtained by enzymatic kinetic resolution of acetylated precursors in three or four steps with cyanohydrins as key intermediates.
Tetrahedron: Asymmetry 1993,4.903
Enzymatic Resolution of Aziridiie-Catboxylates. MariaBucciamlli,ArrlgoForni, Irene Moretti*,Fabio Prati and GiovanniTone Dipartimentodi Chin&a dellWaivenita’,via Campi, 183,41100,Mcdeaa, Italy.
N-acyl-aziridine-2-carboxylates and N-acyl-aziridine-2,3dicarboxylates have been resolved with good to excellent stereochemical purity by enzymatic hydrolysis catalyzed by lipase from Candida cyhdracea. COGCH, (-)-(%3R)
6)-W H r
R = CH3; n.C3H7
COOCHB
COR
Tetrahedron: Asymmetry 1993,4,907
ENZYME REACTIONS IN AFOLAR SOLVENT. 6. THE EFFECT OF DOUBLE BOND ISOMERISM ON THE RATE OF PPLOAT~Y~~DAOYLATI~N OF ALLYLIC ALCOHOLS Brian Morgan #* and Allan C. Oehlschlager Department of Chemistry, Simon Eraser University, BurnabyB.C.. CanadaVSA IS6
Pancreaticporcine lipase (PPL) preferentiallyesterifies the (E)- isomers of lo and 2’ allylic alchohols. R? %
OH
PPL R4
+
Triflouroethyi butyrate
Rl
...
x111
ENZYb5cATALyzED
C ACYLUION AND HYDROLYSISOF
QRUVATIVESzCQNTRIBUTlON Tetrahedron: Asymmetry 1993,4,911 TODJWELOPMENT OFMODFXS F$R REACITONS CATALYZED BYPORCINE LIVEREsFERASEANDPORCINE PkNCREWCUP/GE Koichixo Nacmura,* Ritsuko Fuw, Nobuo Takahasbi, Masayosbi Konisbi, Yoshiki HIrose, and Yosbito Tobe Department of Chemistry, Faculty of Engineering Science, Osaka University, Toyonaka, Osaka 560, Jqmj Lipase YS catalyzed acyiation of #be c&-dial 2 in cyclohexa~ gave the cismonogcttate f-)- 3 and PLE, PPL, &ase YS, and CCL catalyzed hydrolyses of the kdiacetate I gave also optically active 3. c&2,5-DISUBSTTWfRD
lipase YS,
PLE,
CCL
(-J&C in butfer solution A@
,
OAc
PPL
in buffer
w
SOh.#i&
Tetrahedron: Asymmetry X993,4,919 Separation of Stereoisomerik l.l’-Bis(a-hydroxyethyl)ferrocenes by Lipase-Mediated Acetyl+ion in Organic Solvent D. Lambusta, G. Nicolosi,*’ A. Patti and M. Piattelli Istituto CNR Studio Sostanee Naturali, Via de1 Santuario 110, 95028 Valverde CT, Italy H
CHa OH
FO
+ CUa=CH-OAc.
-
~
~~
~~
OH
4 ”
Ha
P~ez&monas
CHa
cepaciu lipas
CHa
in acetone allows the separation of (R,R)-, (S,S)- and (R&-isomers of I,1 ‘-bis(a-hydroxyethyl) i:errocene.
Tetrahedron: Asymmetry 1993,4,925 RESOLUTION OF DIOLS WIWH C -SYMMETRY BY LIPASE CATALYSED TRANSESTERIFICATION 3 , andTorbj6m Norin’ Huit AI&s h4atWn’. Niias OhmeG, Department of ~~~ andBio~~~~z ~~~t~~~~~* Royal Jnstitute of Technology,S-lF 44 Stcckholm,Sweden Theresolutionof dialswithCz-symtnetryby lipasecatalysedtramestetificatioc wasdemonstmted. Thedials wereobtainedin high vields with99% ee in mastcases.
Tetrahedron: Asymmetry 1993,4,93 1 SELECTIVE LIPASE-CATA YZED ACYLATION OF 4,6-0.BENZYLIDENE-D-GL COPYRANOSIDESTO SYNTHETICALLY USEFUL $STERS via L&i Panza,a Sara BrascaP S ‘o Rivab and Giovanni Russ@ 0 ~iflrytinrtno di cwcu &gmica c kdwtriak Venniaa,21 - 20133 Mikmo - ItalR. Is&to di Ckmicu &gli Orrnoni,ChWvia Maria Bianco, 9 -20131Milan0 - Iit+ Lipase-catalyzedregiosektive ztcylationofmethyl4,6-O-benqkiene-a- and P-D-gk.opyranosiQs is de&be& Ph
~iosee P _Ph Activated ester
xiv
1
Tetrahedron: Asymmetry1993,4.933
EnzymaticResolutionof Acylatesof Pm&al Phenolicl-A+ and l-ArylaUryl-l,2,3,4Jy~~~o~ls, whichpossessa GuaiacoltypeMoiety,by use of ImmobilizedLipasein mic Solvent OsamuHo&in~,*~RukaTaaahashi,aMitauhimOkxia,a HiroyukiAkitap andTake& OishiC Facultyof Pharm.Sciences,ScienceUniversityof Tokyo, Shinjuku-ku,Tokyo 16za Facultyof Pharm.Sciences, TohoUniversity,Miyama,Funabashi-shi, Chiba274;b MeijiCollegeof Pharmacy,Setagaya-ku,Tokyo154,cJapan Kineticresolution using lipase immobihed
S-. 6- or 7-OA.z
with c&e
U-854 (2%%.a$ GmR)
8.76% (5.72%ez) Pm.9 a: lip&?.organicsolvent
yy$&y (n=O. 1,2)
in organic solvent was carried aa.
Tetrahedron: Asynmetry 1993,4.943
Immobiization of Substrates in Ewyme-Catalyzed Hydrolysis
Chi-Hsin R. King and Alexey L. Margolin*, Marion Merrell Dow Research Institute, 2110 E.Galbraith Rd. ,Cincinnati, OH 45215 USA A new technique - immobilzation of substrates on solid supports - was applied to the synthesis of a new potent optically pure serotonin receptor antagonist (R-l).
Tetrahedron: Asymmetry1993,4,947 An Enzyme-Based Synthesisof(S)_(+3-Methyl-2[(phenylsuIfaay?am?thyllbutyl Phenyl Sulftie and the Stereocbermcrl Course of its Alkylation RouanGuevel and Leo A. Paqueue* EvansChemicalLdnmtories, The OhioStateUniversity, Columbus, Ohio 43210 Lipase P-30 hydrolysis of 9 finds the (,Y)-
oLa
enantiomerto be lessreactive. Conversion of this material (>95% e.e.) to (-)-11 was
followed by highly diastereoselective akyk tion to give, for example, (-)-W.
H Qw
w?m
m
AJ H’
-
IPll (g-11
(-)-O
J&? m
-
Ii
km (g-13
I
Dimtare andEaatio&lectin Bstuifii
Lipapeflom-fl-ns. Ki$alS.BisbtandViiS.Parma+
Enantband-vcacety~on of racemicplusmcs&&ne2,3-diol.
of Butatw23diol Catdysedby tk
Tetrahedron:Asymmetry 1993,4,957
1
Enzyme catalysed resolution of aminophosphoaic acids - I .
Tetrahedron:Asymmetry 1993,4,959
Setin and Isoserin analoguea
A. Hais@, C. R&ilk@. R. Douilb% N. Goaloa? G. Htt8ebb andF. Levaya@ ~LabpntoiradcRMNetde~v~~~~4722~&l~~~,F~2N~~~~~) IashIatflir AaOr8aaischa cbcmia und.%ktamhe&, I-LH&e-KJaivasittt,IJaiv~it&ss@c1,Dm
Cd-&fit)
K,IU A
1 2
0
R
0
a4
R’ viilwtalc PI tipas
R=-P(O)(OMe~.R’=H 34%1eonversion R=H.r=-P(o)(oE& -
MISSBLDGRJ1(GERMANY)
Roduclobtained
R
C&0G
I”Y I HOCOCH, No eaaatios&ctivity
84mGgumtianonly (cc 0 1c0%)
Enzymatic Resolution of Bulanoic Esters of 1-Phenylmethyl 1-[2-Phenylethyl] Ethers of !3-Chloro-1 ,P-Propanediol
and
Tetrahedron:Asymmetry 1993,4,961
Vaasilia Par&, Viggo Waagenl, Thor Al& and Thorleif Anthonsen’ 1, Department of Chemistry, Thtj University of Trondheim, N-7055 Dragvoll, Norway 2, Borregaard Fine Chemicals, P.0. Box 256, N-1701 Sarpsborg, Norway
I
rat
R = CH,Ph,
E=15 R = CH,CH,Ph, E=25
s
f?
--
ENZYME- CATALYSED ESTEdlFlCATlON OF Tetrahedron:Asymmetry 1993,4,969 (*) - TRANS - CYCLOHEXANE : 1.2 - DIMETHANOL. Stanley M. Roberts’, Vemnique 0. R. Steukers’ and Philip L. Taylo? ‘Departmentof Chemistry, University of Exeter, Exeter EX4 4QD, Devon, UK, *Research Department, ICI Paints Division, Wexham Road, Slough SL2 5DS, UK A Lipozymecatalysed esteriticatioa process produced diester (A) in ca 83% ee.
Tetrahedron:Asymmetry 1993,4,973 C BLOCKS USING PSEUDOMONAS FLUORESCENS SYNTHESIS OF CHIRAL BUIL C HYDROLYSIS OF hfES0 DIACETATES LIPASE CATALYZED ASYMM Zhuo-FengXie, Him&iSuemuneI? 4 KiyoshiS&a?’
Facultyof Pharmaceutical Sciences;gyushuUniversity,Fukuoka812,Jspn
Aed)(2oAe Ii Me
-pFL
IHeAc
Ac&AF
(>99% e.e., 33%)
“C&OAc
(96%e.e., 79%)
xvi
Highly Asymmetric Enzymatic Hydrolysisand Transest&icatioa of mtso-Bis(acetoxymetbyl)and Bis(hydroxymctbyl)cyclopentane i)criv&es: An Knsigbt into the active Site Medel of Rkiropns MarahsmTan&a,MikiYoshioha,andKiyeshiSahai* Fady
ofPhammceukal
I D&mar
Sciences. Kywhu Univertiry.Fukuoka
Tetrahedron: Asymmetry 1993,4,98 1
Lipase
812,Japan
RDL- or PFL-catAysal
hydrolysisof mw-dimetate a&&d the chhaimoneawate (>99%ee).whichwasccovened into the (-)&steromycin. 4Hs
>99%ce (-)-Aristeromy
RDL A= Ao (0rPPL)
HO OH
Tetrahedron: Asynmetry 1993,4,997 STUDIES ONTHE ENANTIOSELECTIVITYOF THE TRANSESTERIFICATION OF 2-METHYL1,4-BUTANEDIOL AND ITS DERIVATIVES CATALYZED BY Pseudomonusj7wrescen LIPASE IN ORGANIC SOLVENTS. P. Grisenti,P. Ferraboschi,S. Casati,E. Santaniello* Dipartimentodi Chimica e Biochiiica Medics, Universita’di Milano,50-1-20133,Milano,Italy The irreversible txansestetitkation catalyzed by Pseudomonasjluorescens lipase has been used for the resolution of racemic 2-methyl-1,4-butanediol la and its benzyl ethers 29 and Ja, the best ee having been obtained for 2a (z.9896).
“OJ-LHPh HOdO”ehCH20J-LOH Tetrahedron: Asymmetry 1993,4,1007
Factors affecting the lipnse catalyzed lransestwl5.
cationrescttonxat 3hydroxy estenrtn otgsnic selventa.Uwe Bomchewr, Nagoya Univwity, DcpLcP Focd Scienceand Technology,Furc-cbo,Chikuu-ku,Nagoya 464-01, Japo,
AndreaHerar,L.am Kreye,VclkorWend4 An&em Capewell,Inrt Teoh.Ckem.Callinrtx3,300O Hannover1, Germany,HamnutH. Meyer,Inst.Org. Chem.,SchneiderberglB, 3000 Hanacvw 1, Germany,‘TlmmasScheper’,Inat Bicchem.Abt. Biotecbnclogie,IJniveniQtMUnrter,Wilhelm-Klamm-Str. 2,440O Miinrter,Germany, F&kc% N. K&ii, Dept Chem.En&,NationalTechniul Univenily Athena, Zogra~cu Cdmpur,15700 Athena,Gmcce. Tbe enaatioselectiviiy of rmnr&wifica~Icn reactionawith 3-hydmxyeaten in several organicsclvenb couldbe influencedandchangedby rclvent,lipae and acylatingagent.Reactionswere alsc performedat controlledpH, water contentandw&r a&&y. Kineticstudieswere performedin the optimizedsystem resultingin sub&rateinhibitioncausedby PIIcxcss of vinylacetateandthe slow reacdngenantiomarof therxemic 3-hydrcxyester.
of
,uaR,
+,.Ao,,,,
“pm0
b
R
‘u,,
+
R”‘.OH
organic sohrsnt
Enzyme
Assisted
Synthesis
of
Enantiomerically
Pure
Tetrahedron: Asymetry 1993,4,1017
CLactones BernhardEaase and Ma&d P. Schneider’,FB 9 - BetgischeUnivetsit&CiH-Wuppcual,B-5603Wuppcrtal 1. Germany
xvii
Tetrahedron: Asymmeny 1993,4,1027
Lipase Catalyzed Formation of Lactones via Irreversible Intramolecular Acyltransfer MarioLobe.11 and ManfrcdP. Schnci&r*, FB 9 - BergischeUniversitit-GH-Wuprtal,
W-5600 Wuppertal 1,Gemmy
lipase from
C&13 Y
H ‘:
Pseu4kmona.s sp.
(CH2)10 ‘COOCH=QI, OH
(+)-3f
cdl13
&
moIecuhu sieves 4 A hexane 66’C, 24 h
0 cz
(R)-4f 32 % 0
1 I
1 Tetrahedron:Asynmetty 1993,4,1031
Pen G Acylase Catalyzed Resoltttion of Phenylacetate Esters of Secondary Alcohols. E. Baldarog, P. D’Arrigo, G. Pedrocchi-Fantoni, C.M. RoselI#, S. Servi A. Tagliani and M. Terreni. Dipartimento di Chimica, Politecnico di Milano, Italy, 8 Rccotdati, S.p.A. De.Bi.Milano, Italy, #Institute de Catalisis y Petrolquimica, Madrid, Spain. OH
Pen Gi acyiase Ph--?f”yR 0
1
-b
PbT”YR
+
R’
R’
Tetrahedron:Asymmetryl!B3,4,1035
Enzymaticresolutionsin 3-aniino-1.2~propane4liol series M.-A. Mbapp6and S. Sicsic Biocis-CNRS,Faculti de pha@acie,Chatenay-Malabry,922%, France. A-i_ OCOR H 2
A
-OH AcNH ?iH
+
ATOCOR OH
i: hydrolysiswithE30000,iixcylationwithbeefliveracetonepowder The re.solutionof 3-amino-1,2propane&iol derivativeshas been carriedout by way of enzymaticcatalyscd hydrolyses or acylations.
Tetrahedron: Asymmetry1993,4. 1041
Enzymatic Resolution of ;N-Dialkyl-3-hydroxy-4pentenamides, Unsuccessf r I in Resolution by the
Katsuki-SharDless
Asyhmetric
Epoxidation
Hiroki Takahata,* Y&mhiro c da, Yoshie-Ohkawa, and Takefumi Momose* Faculty of Pharmaceutical Scie? ces, Toyama Medical & Pharmaceutical University, Sugitani 2630, Toyama 930-01, Japan On OH immot$l/zed
R’R2N
fi
lipase
) 0 1
vinyl acetate pentane
R’R2N
fi
0 (W-1
...
xv111
.
+
.,2N4y (SW
1
EnantiocomplementaryPreparationof OpticallyPure 2-Trimethylsilylethynyl-2cyclopentenolby Homochiiion of RacemicPrecursors: A New Route to the Key Intermediateof 125~Dihydroxycholecalcif&andViiine SeiichiTakano,’ Mahito Suzuki,and Kunio Ogasawara PharmaceuticalInstitute,TohokuUniversity,Aobayama,Sendai 980,Japan
4 Mitsunobu
1
1Mitsunobu
R= --TM
reaction
Tetrahedron:Asynmwy 1993,4,1043
4
reaction
STEREOSELECTIVE HYDROLYSIS of SUBSTITUTEDCYcLoPJ?NTANE DIESTRRS with PIG LIVRR ESTEIUSE @LE).
Tetrahedron: Asymmetry 1993,4,1047
Peter Renold and Christoph Tamm Institut fti Organ&he Chemie der Universitit Basel, St. Johanns-Ring 19, CH-4056 Basel, Switzerland $+zIM@G~;~z;~
Compounds 2,3,4a, Sa, 6a and
7a were hydrolysed by PLE (e. e. values 6-73%).
R2 4a R’= 0H,R2=CH20H 6a R’ - CH20H, Rz = 3H
Terrahedron: Asymmetry 1993,4,105 1 10666 N. TorreyPines Rd., La Jolla, CA 92 037USA OH 0
Pseudomonas lipase
OH 0
OAc0
Lii-catalyzed
resolution of 3-hydroxwic acid and glycosylatioausing gluwsyl phosphite as reagent
Preparation of 6-Deoxy-6,6,6-trifluoro-D-mannose and n-Allose from Enzymatically Resolved 2-Butenolides
Tetrahedron: Asymmetry 1993,4,1059
TakashiYamazaki,*Kenji Mizutani,and TomoyaKitazumd Departmentof Bioengineering,TokyoInstitute of Technology,Nagatsuta,Midori-ku,Yokohama227, Japan
xix
Tetrahedron: Asymmetry1993,4,1063
NITRILE OXIDES IN MEDICINAL CHEMISTRY. 5. LIPASE PS-CATALYZED RESOLUTION OF A SET OF HETEROCYCLIC DERIVATIVES.
Giacomo Camea,’Paola L.iverani.Sergio Riva, fstituto di Cbimica degli Ormoni. C.N.R. -Via Mario Bianco.9 - 20131 MILANO (IMY) MarcoDe Amici. Carlo De Micheli, Marta Camielli. Dipartimentadi Science Farmaceudche,UniversiP di [email protected]=TE (Italy). Br
)-x I
lipase PS
OCOGH7
h”Ef&
N\O (*)
*
I>OH
+
(R)-(-): e&.=94%
k-&_$, (S>(+): e.e. >99%
Lipase from Pseudomonas cepacia (lipase PS) catalyzed the hydrolysis of a series of buyrates of primary alcohols carrying a A2-isoxazolineor an isoxaaolidin-3-onenucleus.
CHEMOENZYMATIC SYNTHESIS OF ACETYL (R)-(t)- AND (S)-(+CYCLOSERINE
Tetrahedron: Asymmetryl!B3,4,1073
Marco De Amr~. Carlo De Micheli.’ FraocescaCateni. Dipartimentodi Scienm Farmaceuciche. Universitsdi Trieste.34127 TRESTE (Italy). Glacomo Carma. Gianluca Ottolma. fsrimlodi Chimica degli Ormoni. C.N.R. - Via Mario Biaoco.9 - 20131 MdanOWyl. BzlO
OCOCsH,
~OGH7
N/ ‘? ‘0 (f)
lipase CV “E”;;
-“‘ouon
+ e.e. >99% (RI-(+)
Bdoj-J e.e. >9?w (Sk(-)
xx
The IWOenantiomers of acetyl cycloserine were prepared in e.e. >98% through Ihe hydrolysis of 3-benzyloxy-4-hydmxy-A*~jsoxazoline botyrate under the catalysis of lipase from chromebocrerium viscosum. The reaction spontaneously Sloppedat 50% conversion of the substrate,