Handbook of Biotransformations of Aromatic Compounds

618 Pages·2004·6.3 MB·English

by  B.L. Goodwin

Handbook of
BIOTRANSFORMATIONS OF
AROMATIC COMPOUNDS

Handbook of
BIOTRANSFORMATIONS OF
AROMATIC COMPOUNDS
B.L. Goodwin
CRC PR E S S
Boca Raton London New York Washington, D.C.
LibraryofCongress Cataloging-in-Publication Data
Handbookof biotransformations ofaromaticcompounds /BrianL. Goodwin.
p.cm.
Includesbibliographicalreferencesandindex.
ISBN0-415-27176-2 (alk.paper)
1.Aromatic compounds—Metabolism. I.Goodwin,BrianL.
QP801.A75H362004
572?.5—dc22 2004045488
Thisbookcontainsinformationobtainedfromauthenticandhighlyregardedsources.Reprintedmaterialis
quotedwithpermission,andsourcesareindicated.Awidevarietyofreferencesarelisted.Reasonableefforts
havebeenmadetopublishreliabledataandinformation,buttheauthorandthepublishercannotassume
responsibility forthevalidityof allmaterials orforthe consequences of theiruse.
Neitherthisbooknoranypartmaybereproducedortransmittedinanyformorbyanymeans,electronicor
mechanical, including photocopying, microfilming, and recording, or by any information storage or
retrieval system,without prior permission inwriting fromthe publisher.
The consent of CRC Press LLC does not extend to copying for general distribution, for promotion, for
creatingnewworks,orforresale.SpecificpermissionmustbeobtainedinwritingfromCRCPressLLCfor
suchcopying.
Direct allinquiries toCRC PressLLC,2000N.W.Corporate Blvd.,Boca Raton, Florida33431.
TrademarkNotice:Productorcorporatenamesmaybetrademarksorregisteredtrademarks,andareused
only foridentification andexplanation, without intentto infringe.
Visit the CRC Press Web site at www.crcpress.com
#2005by CRCPressLLC
Noclaim tooriginal U.S. Governmentworks
InternationalStandardBookNumber 0-415-27176-2
Libraryof CongressCardNumber 2004045488
Printed inthe United States ofAmerica 1 2 3 45 6 7 8 90
Printed onacid-freepaper
Contents
Introduction
Part I Reactions of Individual Compounds (A(cid:1)Z) A1
/
Part II Enzymes and Reactions 1
1. Reactions involving the formation and degradation of the aromatic
nucleus 5
1.1 Aromatization of 6-membered carbon and heterocyclic rings 5
1.2 Formation of carbon ring systems 10
1.3 Formation of heterocyclic ring systems 12
1.4 Polymerization reactions 17
1.5 Reactions involving carbon ring fission 18
1.6 Reactions involving heterocyclic ring fission 25
1.7 Dearomatization 30
1.8 Ringexpansion 32
2. Oxidations and reductions involving the aromatic nucleus and
non-organic substituents 33
2.1 Hydroxylation of the aromatic nucleus 33
2.1.1 Hydroxylations associated with physiologically important
amino acids and hormones 33
2.1.2 Hydroxylations of natural products and miscellaneous compounds
associated with normal animal physiology 40
2.1.3 Hydroxylation of xenobiotics 48
2.1.4 Hydroxylation with elimination of substituent 52
2.2 Formation of quinones and analogues from catechols, quinols and other
precursors 57
2.2.1 Tyrosinase and unspecified types 57
2.2.2 Enzymes classified as laccase and quinol oxidases 59
2.3 Free radicals from phenols 62
2.4 Oxidation of nuclearamino groups and analogues 62
2.5 Oxidation of heterocyclic amines 65
2.6 Reduction of nitro groups and analogues 65
2.7 Oxidation and reduction of sulphuratoms 69
2.8 Reduction of quinones and analogues 70
2.9 Halogens and the aromatic nucleus 71
2.10 Epoxide formation and reduction 74
2.11 Deamination ofarylamines without hydroxylation 75
2.12 Dehydroxylation of phenols 75
2.13 Nitro group addition and removal 76
v
Contents
3. Oxidations and reductions of substituent side chains and non-aromatic
ring systems (without altering chain length) 77
3.1 Hydroxylation of the carbon side-chain 77
3.2 Alkyl oxidation to ketone 82
3.3 Oxidations and reductions of alcohols, aldehydes and ketones 82
3.4 Reductions of acids 92
3.5 Deamination 93
3.6 Oxidative removal of substituents on amino groups 100
3.7 Oxidations and reductions involving nitrogen atoms 102
3.8 O-Dealkylation 104
3.9 Oxidations and reductions of non-aromatic ring systems 106
3.10 Sulphur replacement 109
3.11 Dehydroxylation 110
3.12 Side chain halogenation 110
3.13 Oxidative rearrangement 110
4. Formation and degradation of side-chains 111
4.1 Side-chain formation 111
4.2 Decarboxylation reactions of phenolic groups without hydroxylation 114
4.3 Decarboxylation reactions of side-chains 115
4.4 Other reactions involving side-chain shorteningand removal 122
4.5 Chain lengthening reactions 127
5. Conjugation and substitution reactions 130
5.1 Ester formation A. Carboxylate esters 130
B. Sulphate esters 135
5.2 Sulphamate formation 139
5.3 Glycoside formation 140
5.4 Conjugation of thiols 150
5.5 Formation ofamides and substituted amides 156
5.6 Phosphorylation reactions 164
5.7 Ether formation 165
5.8 N-Alkylation 172
5.9 Silane anhydrides 174
6. Elimination of substituents 175
6.1 Ester hydrolysis 175
6.2 Hydrolysis of glycosides 180
6.3 Hydrolysis ofamides 184
6.4 Hydrolysis of phosphates 190
6.5 Miscellaneous reactions 191
7. Transfer reactions 193
7.1 Transamination 193
7.2 Isomerization 199
7.3 Migrations 201
7.4 Racemization 201
vi
Contents
8. Formation and reactions of non-aryl double and triple bonds 203
8.1 Double and triple bond formation 203
8.2 Reactions of double bonds 205
9. Hydration of epoxides 208
10. Light-forming reactions 211
Bibliography 213
Index (cid:1) Part II (enzymes and reactions) 567
/
vii

Author Biography
Brian Goodwin, D.Phil., is retired. He received his M.A. in natural sciences from Cambridge
University, England and hisD.Phil., fromOxfordUniversity, England. Heworked as a researcherin
thepharmaceuticalindustry(1958(cid:1)1961),researchworkerintheDepartmentoftheRegiusProfessor
/
ofMedicine,OxfordUniversity(1961(cid:1)1967),visitingresearchworker,FelsResearchInstitute,Yellow
/
Springs, Ohio (1967(cid:1)1969), Principal Biochemist, Queen Charlotte’s Maternity Hospital, London
/
(1969(cid:1)1991), Research scientist, Royal Botanic Gardens, Kew, London (1991(cid:1)1993) and Senior
/ /
Research Fellow, King’s College London (1994(cid:1)1997). He is also a qualified horticulturist and
/
preacher.
Dr Goodwin’s main research interests havebeen the metabolism of aromatic amino acids and
aminesandtheirconnectionwithdisease,themetabolicpathwaysofaromaticsandthedevelopmentof
potential drugs.
DrGoodwinisaMemberoftheBiochemicalSocietyandaFellowoftheRoyalSocietyofMedicine.
ix