organic reaction mechanisms 1982...organic reaction mechanisms 1982 an annual survey covering the...

ORGANIC REACTION MECHANISMS 1982 An annual survey covering the literature dated December 1981 through November 1982

Edited by

A. C. KNIPE and W. E. WATTS, The New University of Ulster, Northern Ireland

An Interscience @ Publication

JOHN WILEY & SONS Chichester - New York * Brisbane * Toronto - Singapore

ORGANIC REACTION MECHANISMS * 1982

ORGANIC REACTION MECHANISMS 1982 An annual survey covering the literature dated December 1981 through November 1982

Edited by

A. C. KNIPE and W. E. WATTS, The New University of Ulster, Northern Ireland

An Interscience @ Publication

JOHN WILEY & SONS Chichester - New York * Brisbane * Toronto - Singapore

Copyright 0 1984 by John Wilcy & Sons Ltd.

All rights r w m c d .

No part of thin book m y be reproduced by any means. nor transmitted, nor translated into a machine language without the written permission of the pubhher.

Library of Congress Catalog Card Number 66-23143

British Library Cataloguing in Publication Data: Organic reaction mechanisms.-l982

1. Chemistry, Physical organic-Periodicals 2. Chemical reactions-Periodicals 547.1'394'05 QD476

ISBN 0 471 90202 0

Phototypeset by Speedlith Photo Litho Ltd., Manchester. Printed at the Pitman Press, Bath, Avon.

Contributors D. BILLINGHAM

J. BRJZNNAN

C. CHATGILIALOGLU

D. J. COWLEY

M. R. CRAMPTON G. W. J. FLEET

M. C. GROSSOL

A. F. HEARTY

A. J. KIRBY R. B. MOODIE C. J. MOODY

A. W. MURRAY

M. I. PAGE

R. M. PATON

J. SHORTER

Department of Pure and Applied Chemistry, Strathclyde University, Glasgow

Department of Chemistry, University of Manchester Institute of Science and Technology

Istituto dei composti del carbonio, Consiglio Nationale delle Ricerche, Bologna, Italy

School of Physical Sciences, New University of Ulster

Department of Chemistry, Durham University Dyson Perrins Laboratory, South Parks Road,

Department of Chemistry, Bedford and Royal

Department of Chemistry, University College,

University Chemical Laboratory, Cambridge Department of Chemistry, University of Exeter Department of Chemistry, Imperial College of

Department of Chemistry, University of

Department of Chemical Sciences, Hud-

Department of Chemistry, University of

Department of Chemistry, University of Hull

Oxford University

Holloway College, Egham, Surrey

Dublin, Ireland

Science and Technology, London

Dundee

dersfield Polytechnic

Edinburgh

The present volume, the eighteenth in the series, surveys research on organic reaction mechanisms described in the literature dated December 1981 to November 1982. In order to limit the size of the volume, we must necessarily exclude or restrict overlap with other publications which review related specialist areas (e.g. photochemical reactions, biosynthesis, electrochemistry, organometallic chemistry, surface chemistry and heterogeneous catalysis). In order to minimize duplication, while ensuring a comprehensive coverage, the editors conduct a survey of all relevant literature and allocate publications to appropriate chapters. While a particular reference may be allocated to more than one chapter, we do assume that readers will be aware of the alternative chapters to which a borderline topic of interest may have been preferentially assigned.

With this volume, we welcome as new contributors Drs. Alberti, Billington, Brennan, and Chatgilialoglu. We also take this opportunity to congratulate Dr. Kirby, a contributor to this series since 1976, on his well-deserved selection for the 1982 Royal Society of Chemistry Award which recognizes contributions to the understanding of organic reaction mechanisms.

Once again we wish to thank the publication and production staff of John Wiley and Sons and our team of contributors. We are also indebted to Dr. N. Cully who compiled the subject index.

A. C. K. W. E. W.

vii

Contents 1 . Reactions of Aldehydes and Ketones by M . I . Page . . 2 . Reactions of Acids and their Derivatives by A . J . Kirby

3 . Radical Reactions 1 by C . Chatgilialoglu . . . . 4 . 5 . Oxidation and Reduction by G . W . J . Fleet . . . . 6 . Carbenes and Nitrenes by C . J . Moody . . . . . 7 . Nucleophilic Aromatic Substitution by M . R . Crampton

8 . Electrophilic Aromation Substitution by R . B . Moodie . 9 .

Radical Reactions 2 by D . J . Cowley . . . . . .

Carbonium Ions by M . C . Grossel . . . . . . 10 . Nucleophilic Aliphatic Substitution by J . Shorter . . 11 . Carbanions and Electmphilic Aliphatic Substitution by J . 12 . 13 . 14 . 15 . Author Index, 1982 . . . . . . . . . . . . Subject Index, 1982 . . . . . . . . . . . .

Elimination Reactions by A . F . Hegarty . . . . . Addition Reactions-1 . Polar by D . Billington

Molecular Rearrangements by A . W . Murray

. . . Addition Reactions-2 . Cycloaddition by R . M . Paton .

. . .

. . .

. . .

. . .

. . .

. . .

. . .

. . .

. . .

. . .

. . . Brennan

. . .

. . .

. . .

. . .

. . .

. . .

. 1

. 19

. 73

109

145

. 189

. 211

. 231

. 245

. 263

. 293

. 311

. 331

. 347

. 381

. 479

. 527

ix

Organic Reaction Mechanisms 1982 Edited by A. C. Knipe and W. E. Watts 0 1984 John Wiley & Sons, Ltd.

CHAPTER 1

Reactions of Aldehydes and Ketones and their Derivatives

M. I. PAGE

Department of Chemical Sciences, Huddersfield Polytechnic

Formation and Reactions of Acetals and Ketals . Hydrolysis and Formation of Glycosides .

Non-enzymic Reactions . Enzymic Reactions .

. Schiff Bases and Related Species Oximes, Hydrazones, and Related Compounds

Reaction and Formation of Nitrogen Bases .

Aldol and Related Reactions . Otber Addition Reactions. Enolization and Related Reactions . Hydrolysis of Enol Ethers and Related Compounds Other Reactions . References .

. 1

. 3

. 3

. 3

. 4

. 4

. 6

. 7

. 7

. 10

. 12 * 12 . 13

Formation and Reactions of Acetals and Ketals' As previously shown, the Brransted a-exponents decrease (from 0.7 to 0.5) as the basicity of the leaving group decreases in the general-acid-catalysed hydrolysis of ethylphenylbenzaldehyde acetals. Previous models for proton transfer have been extended and the Brranstedcoefficient has been concluded to be a measure ofthe ease of C-0 bond cleavage rather than the degree of proton transfer, because the latter is assumed to be either zero or unity.2

The bicyclic ketal (l), with an equatorial leaving group, is estimated to hydrolyse 10l2 times more slowly than the monocyclic ketal (2) with an axial leaving group. This presumably results from geometrical constraints to resonance stabilization of the intermediate carbocation formed from (l).3 The acid-catalysed hydrolysis of aldal acetals (3) proceeds, as expected, by the A1 mechani~m.~

2 Organic Reaction Mechanisms 1982

Hemiacetal is an appreciable product of the acid hydrolysis of dimethylformal in water. This explains the inaccuracies observed in the kinetics of hydrolysis determined dilatometri~ally.~

Hemiacetal esters are more reactive than either acetals or acylals because they have a better leaving group or form a more stable carbocation intermediate, respectively.6

The 2-methoxyethoxy group may be selectively cleaved from mixed acetals in their reaction with allylsilanes in the presence of titanium tetrachloride to give homoallyl ethers; this has been attributed to metal-ion coordination to the methoxy and acetal oxygens.'

Addition of hydroxide to the 4-hydroxyflavylium ion gives the relatively stable hemiacetal (4) followed by a rapid equilibration with the ring-opened chalcone.'

It has been claimed, yet again,g that the formation of 1,3-dioxolanes cannot proceed by the 5-endo-trig ring-closure simply because this violates Baldwin's rules."

The pH-independent hydrolysis of anilide acetals in alkaline solution occurs by simple C-0 bond cleavage. Below pH 10 the acid-catalysed hydrolysis gives benzoate ester, aniline, and methanol by initial nitrogen protonation and rate- limiting C-N bond fission (5) with an estimated rate constant of Hydrolysis of the hemiorthoester intermediate becomes rate-limiting below pH 7." m(- \

( i e A r

Ar-C-OMe I

OMe Ph

The mercury(I1)-catalysed hydrolysis of 2-phenyl-1,3-oxathiolan (6) proceeds via the intermediate formation of a 1 : 1 complex and rate-limiting C-S bond-cleavage to give a rapidly hydrolysed hemiacetal." However, with acyclic OS-acetals the rate-limiting step changes to acid-catalysed hydrolysis of the hemiacetal at high concentrations of mercury(Ir).'

The Hg2 +- and T13+-promoted hydrolyses of the monothioacetal, a-ethoxy-a- ethylthiotoluene, proceed by rate-limiting decomposition of the intermediate hemiacetal (7).14

Neutral mercury(I1) species, such as HgC12, are better promoters of the hydrolysis of monothioacetals than are Hg2+ ions. This has been attributed to intramolecular attack of metal-bound hydroxide on the incipient carbocation intermediate (8) which would be facilitated by a reduced charge on Hg2 + .' However, the addition of anions to Hgz+ will reduce the acidity of coordinated water.

H OEt

(7)

1 Reactions of Aldehydes and Ketones and their Derivatives 3

Unlike the rate-limiting hydrolysis of the hemiacetal in the mercury(1r)- and thallium( II)-promoted hydrolysis of 0,s-acetals, formation of the intermediate is rate-limiting in the presence of silver(1) at low acid concentration.I6 Silver(1) is a 3 x 104-fold better catalyst than copper(1) for their hydr01ysis.l~

Aluminium ions catalyse ketal formation but their activity is limited by their degree of hydration.”

The regioselectivity of the reductive ring-opening of benzylidene acetals of hexopyranosides with sodium cyanoborohydride-hydrogen chloride has been attributed to the steric effects of the Lewis acid (E) (9).19

The exo-phenyl group of dioxolane-type benzylidene acetals isomerizes faster than for the corresponding endo-isomers in the presence of aluminium chloride.” Proton abstraction from thioacetals is facilitated by phase-transfer catalysts.’l

Ring-opening of isopropylidene acetals of carbohydrates initiated by lithium diisopropylamide is dependent upon the structure of the carbohydrate.”

Steric and electronic effects have been used to account for the synthesis of optically pure compounds by enantiotopically differentiating monoacetalization of prochiral dike tone^.'^

Diethyl ketals may be oxidized to carbonates with peroxycarboxylic acids presumably via an oxocarbonium ion inte~nediate.’~

Hydrolysis and Formation of Glycosides

Non-enzymic Reactions Volumes of activation for the acid-catalysed hydrolysis of pyranosides and furanosides parallel entropies of activation and differences suggest that furanosides react by an A2 mechanism whilst the pyranosides follow the more conventional A1 route.”

Isotopic labelling studies of the acid-catalysed hydrolysis and subsequent dehydration of uronic acids to 5-hydroxymethyl-2-furaldehyde are consistent with the intermediate formation of a 1,2-enediol which can dehydrate to an enolizable /3- diketone.26

Reversed micelles of dodecylbenzenesulphonic acid in benzene enhance the rate of hydrolysis of dextrin 285-fold compared with the rate in water.27

The acid-catalysed reaction of sucrose in dimethyl sulphoxide proceeds via the intermediate formation of a carbocation.28

The rate ofmutarotation ofor-D( +)-glucose is catalysed by CuZ(OH),” 2 x lo3- fold more effectively than by Cu(C104)2. This has been attributed to electrophilic attack by hydrated copper ion on the ring oxygen of glucose and attack by metal- oriented water on the aldehydic oxygen.”

NMR studies of the mutarotation of p-D-fructose in acidic solutions of DMSO show that furanose formation occurs 2-3 fold faster than pyranose formation. 30

Unidirectional rate constants for the tautomerization of the tetroses in D 2 0 may be obtained by NMR methods. The interconversion occurs via the intermediate acylic aldeh~de.~’

The rates of isomerization and degradation of maltose in alkaline solution are increased by the addition of ethanol.32

Enzymic Reactions

water. The cellulase-catalysed hydrolysis of cellulose is restricted by the availability of


Stereospecifically double-labelled (2H and ’H) D-fructose 6-phosphate gives chiral acetyl phosphate when catalysed by the thiamine-dependent enzyme, phosph~ketolase.’~

The synthesis of dextran from sucrose catalysed by dextransucrase is thought to proceed via a glucosyl-enzyme intermediate which explains the retention of configuration.’

Reaction and Formation of Nitrogen Bases

Schifl Bases and Related Species Viehe’s salt, the iminium chloride (10) reacts with carbohydrate diols in the

presence of pyridine to give carbonates but forms carbamates stereospecifically when triethylamine is the base. The formation of carbamate has been attributed to the higher pH so that the tetrahedral intermediate is predominantly in the anionic form which adopts theconformation (11) which is thought to favour C(1)-0(2) bond-fi~sion.’~

An internally inconsistent and illogical description of the hydrolysis of Schiff bases has been p~blished.~’

The acid-catalysed hydrolysis of Schiff bases derived from pyrrole-2- carboxaldehyde and substituted anilines shows a Hammett p-value of + 1.7 at the maxima in the pH-rate profile.38

The hydrolysis of Sch8 bases derived from benzophenone and diamines exhibits intramolecular general base catalysis by the tertiary amino group (12), with effective concentrations of 4 - 3 4 M.”

Unlike the imine of 2-hydroxyacetophenone, the N-methylimine of 2‘-hydroxy- 1’-acetonaphthone does not show a reaction of the neutral imine, which actually exists as the zwitterion (13), with hydroxide ion. This has been attributed to the 4.6 units lower pK, of the naphthalene derivative (13) so that at high pH it exists predominantly as the unreactive neutral imine-phenoxide.”

The trb.isformation of the “yellow form” of thiamine in alkaline solution involves ring-opening of the cyclic imine to give the a~nino-aldehyde.~~

The kinetics of the acid-catalysed amino exchanges between Schiff bases in benzene have been reported.42

Relative rates of transamination of tertiary enamines have been The Hammett p-value for amine exchange of imines (derived from substituted

anilines) in ethanol is low (0.33).44 The metal-ion- and pyridoxal-catalysed dealdolation of /3-hydroxyamino-acids

to ketones and glycine proceeds by direct a,fl-C-C bond fission (14) and not via the previously suggested a-deprotonated intermediate which would incorporate D in the prod~ct.~’


Y e

(13)

B:>

(14)

The pro-s hydrogen at the prochiral C(6) carbon of ~-1ysine is specifically abstracted by L-lysine, e-aminotransferase from the Schfl base complex formed between enzyme-bound pyridoxal phosphate and the substrate.46

Aldimine is formed from n-hexylamine and pyridoxal 5'-phosphate at neutral pH, 3 or 4 units below the pK of the amine conjugate acid, because rate-limiting dehydration is facilitated by intramolecular general acid catalysis (15).47 4-Formyl-1-methylpyridinium salts are mimics for transamination reactions with

pyridoxal phosphate. Imine formation from an amine and the aldehyde is followed by prototropic rearrangement and hydrolysis to give the carbonyl derivatives of the original a n ~ i n e . ~ ~

/I-Methylene-DL-aspartic acid (16) is an inhibitor of glutamate-aspartate transaminase by, it is suggested, forming a Schfl base with pyridoxal phosphate followed by tantomerization to give the Michael acceptor which traps an important nucleophilic group on the enzyme (17)."

(17)


The borohydride reduction of iminium salts is stereochemically similar to the reduction of the corresponding ketone.J0

The peroxide (18) reacts in aqueous solution to give, depending on pH, 2- acetamidoacetophenone or 2,3-butanedione and 2-aminophenol. Linear, dioxetane and rearrangement mechanisms appe.ar to be competing near neutral PH.~’

Enantioselective protonation of Schiff bases of a-amino-acids by chiral acids has been attributed to steric effects.52

Schiff base formation from diethylenetriamine and 2-hydroxybenzaldehyde bound to copper(I1) is only twice as fast as that from the free aldehydeaS3

The amine-catalysed transformation of l-substituted 3,5-dinitro-2-pyridones and 1,3-disubstituted acetones to 4nitroanilines and N-substituted 2-nitroacetamides proceeds by the intermediate formation of an isolable e r ~ a m i n e . ~ ~

The kinetics of the hydrolysis of cyanuric chloride, C13C3N3, to cyanuric acid has been rep~rted.’~

Oximes, Hydrazones, and Related Compounds The general-acid-catalysed addition of phenylhydrazine to pyrrole-2- carboxaldehyde shows a Brnrnsted a-value of 0.90 whereas that for the N - methylpyrrole derivative is 0.35. This has been attributed to bifunctional ~atalysis.’~

Undissociated acids have been found to catalyse the reversible formation of hydrazones in toluene.”

The reaction of hydrazine with tetrazines has been examined.58 The general-acid-catalysed mutarotation of z-D-arabinose oxime exhibits a

Brransted a-exponent of 0.54 and probably proceeds by an addition-elimination pathway. The rate-limiting step is the general-base-catalysed nucleophilic attack of water on the imine conjugate acid. The hydroxide-ion-catalysed reaction is ca. lo6 greater for arabinose oxime than for acetone oxime and this has been attributed to intramolecular attack by alkoxide oxygen.59

The acid-catalysed hydrolysis of the B-lactam antibiotic nocardicin involves rin opening of the p-lactam followed by the slower hydrolysis of the oxime side-chain.

Equatorial attack on bicyclic ketones by hydroxylamine occurs preferentially to axial attack.61

The acid-catalysed reaction of pbenzoquinone oxime with ethanol to give 1- nitroso Cethoxybenzene involves nucleophilic attack on the carbonyl carbon.62

Specific-acid-catalysed hydration of the carbinolamine intermediate is rate- limiting in thiosemicarbazide formation from Cformylpyridine N-oxide at pH 4-7. At lower pH, general-acid-catalysed formation of the intermediate becomes rate- limiting whereas below pH2 it is suggested that formation of the protonated carbinolamine is ~once r t ed .~ ’ .~~

The Hammett p-value for semicarbazone formation from 5-substituted furfurals is 1.68.65

The Hammett pf-value for the reaction of thionyl chloride with 4-substituted acetophenone semicarbazones to give 1,2,3-thiadiazoles is - 0.55, indicative of an electron-deficient carbonyl carbon in the transition state.66

The Mannich reaction of acetophenone with formaldehyde and piperazine is first order in each rea~tant.~’

Tautomerism of hydrazone-enehydrazine is dependent upon substituents.68 The mechanism of reactions of enamines has been reviewed.69

!;

I Reactions of Aldehydes and Ketones and their Derivatives 7

Aldol and Related Reactions Stereoselectivity in the aldol condensation has been r e ~ i e w e d . ~ ' . ~ ~

Intramolecular aldol condensation to give cyclohexenones via a 6-(eno1endo)- exo-trig ring-closure (19) is favoured over the unfavourable 5-(enolendo)-exo-trig process and over all other favoured ring-forming pathways as well.72

(19)

Molecular mechanics calculations have been used to evaluate steric interactions in acyclic aldol transition states.73

The generally accepted chair-like transition state explains the regio- and stereoselectivity of alkenylborane addition to aldehydes.74

The ratio of Cram to anti-Cram diastereoisomers formed upon addition of z- crotylboronate to s-a-methylbutyraldehyde depends on the chirality of the b~ronate .~ '

In the presence of trialkylboranes, lithium enolates react with aldehydes to give predominantly the more stable threo-aldol; this has been attributed to steric effects.

The transition state for the reaction of two equivalents of trialkylaluminium compounds with ketones in hydrocarbon solvents is thought to be an alkyl-bridged six-centred arrangement.7

Tho-selectivity in the aldol formed from tin enolates of cyclohexanone with benzaldehyde can be explained by either the classical chair or boat transition states.78

The stereoselection of the lithium-catalysed aldol reaction of benzaldehyde and a- butyrolactone is reversed by zinc ions. Because zinc readily forms square pyramidal and octahedral complexes with oxygen ligands it is claimed that this coordination geometry can favour erythro-sele~tion.~~

Aldol condensations of optically active a-amino-acids coordinated to copper(I1) with benzaldehyde give fl-hydroxy-a-amino-acids stereoselectively ; predominant formation of the threo-diastereoisomers has been attributed to the formation of an oxazolidine intermediate."

The aldol reaction of alkyl phenyl ketones and benzaldehyde in the presence of hydrogen bromide gives diastereomeric fl-bromoketones under thermodynamic control."

The aldol addition of formaldehyde to 2-hydroxyacetophenone also forms benzaldehyde, benzoic acid, and formose sugars. Retro-aldol products are thought to be accelerators of formose formation.82n In the presence of a strong organic base the Cannizzaro reaction can be suppressed at the expense of the formose reaction which converts formaldehyde to carbohydrates.82b

Acetaldehyde undergoes an acid-catalysed aldol condensation in the gas phase.83

Other Addition Reactions A comparison of solvent effects on rate and equilibrium constants for the reaction of nucleophiles with carbonyl compounds suggests transition states different from


those indicated by Brnrnsted parameters. There is no reason why transition states should be solvated in the same way as stable molecule analogues. The different trends in nucleophilic reactivity toward 9-acetyl-9-cyanofluorene (20) compared with 2,4dinitrophenylacetate may result from a concerted reaction for the ester but a step-wise one for the ketone.84

Hydration of the ketone group of methyl pyruvate to give the gem-diol is catalysed by general bases and by carbonic anhydrase. The Br~nsted !-value for general base catalysis is 0.39, slightly lower than that observed for aliphatic aldehydes, with diethylmalonate dianion showing a negative deviation.”

The reversible hydration of 1,3-dichloroacetone in the presence of non-ionic reversed micelles in carbon tetrachloride shows a positive entropy of activation and proceeds at a faster rate than that in aqueous dioxan; this has been interpreted in terms of the order of micelle-bound water.86

a \

Polyfluorinated B-diketones are hydrated preferentially at the carbonyl nearest the fluorine subs tit uen t .87

l,l,l-Trichloroacetone reacts with ammonia buffers in propanol-water to give mainly acetamide, n-propyl acetate, and chloroform. Ammonolysis occurs mainly through an aldoxide-cgtalysed pathway which it is suggested, with little supporting evidence, may represent concerted general base catalysis (21).*’

The formation constants for cyanohydrins from substituted acetylbiphenyls give a Hammett p-value of 0.52 and are linearly related to the rates of borohydride reduction of the ketones.89

The Hammett p-value for the reduction of alkyl aryl ketones with lithium aluminium hydride is 1.77 consistent with a reactant-like transition state.”

According to ab initio calculations borohydride addition to formaldehyde proceeds via a single-step mechanism with a non-synchronous four-centre transition state with a product-like geometry.”

The lithium aluminium hydride reduction of l-aryl-2-meth 1 1 butanones gives

Mixed solvents cause a much higher asymmetric induction than either of the individual solvents in the reduction of chiral a-ketoamides with sodium borohydride.”

The Hammett p+-values for the reaction of trialkylboranes with substituted benzaldehydes decreases with increasing reactivity of the borane and are consistent with a hydride-transfer mechanism. Entropies of activation indicate a highly ordered transition state.94

Ketols isomerize in basic solution by intramolecular hydride transfer. Cation and concentration dependence of the rates are consistent with the dissociated alkoxide ion being the reactive species.95

stereochemical products predicted by asymmetric induction. L- -


An alternative to the "diamond lattice model" for the liver alcohol dehydrogenase reduction of cyclic ketones has been proposed. The new model rationalizes previously inexplicable stereochemical features.96

Methoxide ions reduce aldehydes lacking an a-hydrogen in the gas phase; the nearly thermoneutral hydride transfer is in competition with the thennoneutral proton transfer.97

The temperature-independent isotope effect k&, of 2.56 and nearly identical inverse a-effects at the n-centres of allylbenzene are consistent with a non-linear transition state for H-transfer in the ene reaction (22) with diethyl mesoxalate. A symmetrically structured (2 + 2) charge-transfer complex is formed initiall~.~'

2-Chlorotropone reacts with lithium diphenylphosphide in THF to give a product in which the incoming nucleophile attacks C(7) to give a tele-substituted product.99

0- 'PPh3

C' 'CH - R4 I CHz-CH\ ,Ph

, i",Ci t.!\D R1/ \,2 R3 I U H ,c-o:

(22) (23)

Solvent effects have been used to suggest that the non-enolizable adamantanone reacts with alkylidenetriphenylphosphoranes by an initial one-electron transfer from the ylide to the carbonyl group. This is a competing pathway in the Wittig reaction of sterically hindered systems where reduction is predominantly observed over the usual olefin-forming reaction. The initial radical ion pair (23) could also be involved in the Wittig pathway leading to olefins."'

Theoretical calculations support the contention that a primary Grignard reagent reacts by a polar mechanism while a tertiary one prefers a single-electron-transfer pathway."'

The first example of total "cis-preference" in the addition of Grignard-like reagents to carbonyl compounds has been reported for allyltin derivatives; this has been attributed to the steric requirements of five-coordinate tin in the transition state.lo2

The stereochemistry of the product ofmethylmagnesium bromide reacting with 1- aryl-2,3-diphenyl-2-methylpropanones is solvent-dependent,lo3 and may be rationalized in terms of a reactant-like transition state.lo4

The reaction of benzylmagnesium chloride with formaldehyde in THF gives 2- phenylethanol and 2-methyl- and 2-(2'-hydroxyethy1)-benzyl alcohol. The decreasing yield of 2-methylbenzyl alcohol with time has been attributed to polymerization of formaldehyde. The diol is formed by reaction of the intermediate (24) with f0rma1dehyde.l~~

Unhindered aldehydes and ketones react initially with benzylic Grignard reagents by a reversible rearrangement.' O6

Unlike most bridged cyclohexanones, bicyclo [3.3.1 Inonan-2-one reacts with methylmagnesium iodide to give preferentially the exo-alcohol formed by axial attack.' O7

The stereochemistry of the addition of organomagnesium compounds to substituted cyclopropyl aldehydes has been interpreted in terms of relative transition-state stabiIities.lo8


Highly effective stereo-control in the reaction of optically active allylsilanes with aldehydes has been interpreted in terms of acyclic linear diastereomeric transition states with both enantio- and diastereo-selectivities resulting from steric interactions in the transition state.'Og

Metal salts influence the stereochemical ath of nucleophilic addition of

The stereoselective synthesis of CC bonds by addition of crotylmetal compounds

The reactions between alkynes and carbonyl compounds in toluene/l5 % aq.

The direction of nucleophilic attack on the thiocarbonyl group has been

organometallics to ( f )-3-phenylbutan-2-one.' P O

to aldehydes has been reviewed."'

NaOH are accelerated by phase-transfer catalysts. l 2

considered using MO theory.'I3

Enolization and Related Rea~tions"~ Six different transition states have been characterized for the enolization of acetone in acetate buffers based on solvent isotope effects and Brernsted exponents. As previously suggested the third-order term including acetate and acetic acid corresponds to a transition state in which the carbon proton is in flight whilst the oxygen proton is transferred in a stable hydrogen bond (25). As the carbon proton is removed, the base strength of the carbonyl oxygen increases and when it is equal to that of acetic acid the proton transfers within a potential energy

The range ofcatalyst pK over which third-order terms are found can be explained by a model based on the Marcus expression. It is suggested that the maximum catalytic advantage to be obtained from the concerted mechanism is only one or two orders of magnitude.'

The degradation of the glucocorticoid cloprednol, an a,a'-dihydroxyketone, undergoes rate-limiting enolization in acidic solution but reversible enol formation under alkaline conditions. This is incorrectly attributed to the rate of product formation from the enol becoming slower than the rate of enolization with increasing pH.'

The pH dependence of the equilibrium constant for hemithioacetal formation from phenylglyoxal and thiols is sigmoidal. The rearrangement of the hemithioacetal to an a-hydroxythiocarboxylic S-ester is general-base-catalysed with a Br~rnsted /3-value of 0.45. Rate-limiting formation of the enediol(26) is consistent with a unit kinetic solvent isotope effect, H20/D20, although there is little rate dependence upon the pK of the thiol."*

The Cannizzaro-type reaction of thiols with phenylglyoxal gives thiol-esters of mandelic acid and proceeds via the intermediate formation of a hemithioacetal. Intramolecular general bases catalyse the reaction by rate-limiting proton abstraction to form the enediol (27)."'

1 Reactions of Aldehydes and Ketones and their Derivatives

0 OH 0 OH It) I II) I

Ph -C-C- SR \I

H

(: B R2N

11

Glutathione specificity for thio-ester formation from a-keto-aldehydes catalysed by glyoxalase I is lost with glutathiomethylglyoxal and the L-isomer of the resulting a-hydroxy-acid is produced. This has been attributed to the binding of the thiohemiacetal intermediate to the enzyme in a manner inverted with respect to the normal mechanism.' 2 o

Assuming that the rate ofreaction of the enolate ion from acetone with I2 and with HOBr is diffusion-controlled the rate constants for halogenation by BrO- and 1 0 - are also large (6-8 x lo7 M - ' s - ~ ) and attributable to rate-limiting formation of a donor-acceptor complex. The pK, of acetone is 18.9 & 0.3, slightly lower than the traditional value of 2O.l2l A value of 19.1 has also been reported, assuming that the rate of reaction enolate ion with HOCl and HOBr is at the diffusion-controlled limit.' 22

The reaction pathway for the acid-catalysed bromination of acetone has been determined by ab initio calculation.' 23

The addition of cyanide to [(methoxycarbonyl)methyl]cobalamin proceeds in at least three steps, rapid formation of a cyanide adduct, cleavage of the C-CO bond to give the enolate anion of methyl acetate in the rate-limiting step and then protonation, preferentially on one face of the enolate, to give methyl acetate. This requires that protonation of the enolate (28) occurs before separation from the cobalamin and that cleavage of the C-CO bond gives an intermediate complex with a life-time of > 10-6s.124

It appears that the enol of acetylacetone is preferentially solvated by methanol whereas the keto form prefers water in mixtures of methanol-water.' 2 5

0 A - (28) (29)

Z = dimethylbenzimidazole

Solvent effects on the tautomeric equilibrium of 5-butyl 2-picolyl and tert-butyl quinaldyl ketones have been interpreted mainly in terms of the hydrogen-bonding power of the solvent.'26

y-Homoenolization is proposed to account for the base-catalysed rearrangement of (29) to (30)."'

Xenon difluoride reacts with steroidal silyl enol ethers to give or-oriented a- fluoroketones whereas iodotoluene difluoride gives the 8-oriented product. This has


been attributed to XeF2 providing electrophilic fluorine whereas the aromatic derivative delivers nucleophilic fluorine.’ 28

The reaction of silyl enol ethers with aminomethyl ethers in acetonitrile is catalysed by iodotrimethylsilane and gives aminomethylation products of the corresponding ketones. The catalyst is thought to generate an electrophilic intermediate (31).12’

The silyl enol ether formed from 3-thia-cyclohexanone has the double bond towards the heteroatom whereas the 3-oxa derivative forms the opposite regioisomer.’ 30

The synthetic utility of a-alkylation of ketones using the corresponding silyl enol ethers and SN1 active alkyl halides has been reviewed.13’

R CH2, /OH

Me, Si ’ Ar \ocHAr ‘X-CH~NR~ ,c=c

Hydrolysis of Enol Ethers and Related Compounds The reactions between aryl methyl ketenes and 1-arylethanols, to give esters, show negative enthalpies of activation (i.e. rate constants decrease with increasing temperature), but extremely negative entropies of activation ( - - 70cal deg- ’ mol- ’). A two-step mechanism has been proposed in which a reversibly formed ketene hemiketal(32) reacts with a second molecule of alcohol.’ 32

High asymmetric induction (99: 1) is observed in the product when tertiary amines act as cata1y~t.s.’~~

The acid-catalysed hydrolysis of a-acetoxyacrolein (33) is slower than for the a- ethoxy deri~ative.”~

R ,CHO

\OAc CH2=C

Other Reactions The pK, determined for protonated ketones depends very much upon the technique employed. Ketones are Hammett bases for the ’H acidity function and rates of enolization may be correlated with this parameter.’ ’’

Calculated proton affinities of 8-substituted benzaldehydes have been correlated with o+-values.’36

Characteristic vector analysis of the protonation of ketones allows the separation of protonation and medium effects. Ketones are intrinsically stronger bases in aqueous perchloric acid than in aqueous sulphuric

The acyloin condensation of aldehydes catalysed by thiazolium ion can be diverted by the addition of flavin which oxidizes the carbanionic intermediate (34) to


a carboxylic acid. Oxidation is very efficient if the thiazolium ion and the isoalloxazine are covalently linked.' 38

The benzoin condensation in aprotic non-polar media is catalysed by bis( 1,3- dialkylimidazolidin-2-ylidenes) by stabilizing the usual masked carbanion (35).' 39

Thiazolium salts covalently bound to chloromethylated polystyrene catalyse the addition of aldehydes to activated alkene~.'~'

Proton release precedes hydride transfer in the oxidation of aldehydes by aldehyde dehydrogenase and the rate-limiting step in the pre-steady-state phase is a conformational change.I4'

The oxidation of ketones by molecular oxygen has been re~iewed.'~' The mechanisms of the Favorskii rearrangement have been reviewed.'43 Substituted diphenyldiazomethanes react with 2,5-dichloro-p-benzoquinone at

vinyl carbon and carbonyl oxygen. The fatter is favoured by electron-donating substituents in the diazo de r i~a t ive . '~~

R I

N OH

[+p< I R'

R

OTf I

I OTf

R - C C - C-CH2 R

Solvent effects in the reaction of phenyldiazomethane with chloranil to give stilbene and spirooxetane have been correlated by linear free energy relationships; the rate constants for the reaction with 2,5-dichloro-p-benzoquinone to give bicyclic dione and polyether increase with solvent polarity and decrease with solvent basicity.'45

The acid-catalysed decomposition of a-diazoketones has been reviewed.'46 The carbonylation of formaldehyde to give glycolic acid is catalysed by copper(1)

and silver carbonyls.' 47

Oxygen-chlorine exchange between aromatic aldehydes and aryldichloro- methanes is catalysed by acids and their anhydrides and suggested to proceed via the intermediate formation of a carbene complex.'48

The chemistry of o-benzoquinone diamines has been reviewed.'49 The formation of vinyl triflates from alkynones and trifluoromethanesulphonic

2-Vinylphenylhydrazonyl chlorides react with sodium azide under phase-transfer

2-Aminopyridines react with 2-haloketones to give cyclic products.' 5 2

The little known thiobenzaldehyde and thioacetaldehyde can be generated from

anhydride is thought to proceed via the intermediate (36).15'

conditions to give cyclic products resulting from a common intermediate.' 5 1

the thermolysis of alkyl thiosulphinates and then trapped with 1,3-dienes.' 5 3

References Bergstrom, R. G., in The Chemistry of Ethers, Crown Ethers, Hydroxyl Groups Their Sulphur Analogues (Ed. S . Patai), Vol. 2, John Wiley and Sons, Chichater, 1980, p. 859. Lamaty, G., and Menut, C., Pure Appl. Chem., 54, 1837 (1982).

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48 Buckley, T. F., and Rapoport, H., J. Am. Chem. SOC., 104,4446 (1982). 49 Cooper, A. J. L., Fitzpatrick, S. M., Kaufman, C., and Dowd, P., J. Am. Chem. SOC., 104,332 (1982). s o Hutchins, R. O., Su, W.-Y., Cistone, F., and Sivakumar, R., Ventron Alembic, 1981,23; Chem. Abs., 96,

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Batalin, D. E., Zh. Org. Khim., 17, 2148 (1981); Chem. Abs., %, 51559 (1982). Counotte-Potman, A., van der Plas, H. C., van Veldhuizen, B., and Landheer, C. A., J. Org. Chem.46, 5102 (1981).

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66 Butler, R. N., and ODonoghue, D. A., J . Chem. SOC., Perkin Trans. 1 , 1982, 1223. 67 Natova, L., God. Vissh. Khim.-Tekhnol. Inst., Sofia, 24, 251 (1981); Chem Abs., %, 5836 (1982).

69 Hickmott, P. W., Tetrahedron, 38, 1975 (1982). 70 Evans, D. A., Nelson, J. V., and Taber, T. R., Top. Stereochern, 13.1 (1982); Chem Abs., 97,54893

71 Heathcock, C. H., Science, 214, 395 (1981). 72 Baldwin, J. E., and Lusch, M. J., Tetrahedron, 38, 2939 (1982). 7 3 Dougherty, D. A., Tetrahedron Lerr., 23, 4891 (1982). 74 Fujita, K., and Schlosser, M., Helu. Chim. Acta, 65, 1258 (1982). 7 5 Hoffmann, R. W., Zeiss, H.-J., Ladner, W., and Tabche, S., Chem. Ber., 115, 2357 (1982). 76 Yamamoto, Y., Yatagai, H., and Marayama, K., Tetrahedron Lett., 23,2387 (1982). 7 7 Ashby, E. C., and Smith, R. S., J . Organomet. Chem., 225, 71 (1982). 7 8 Shenvi, S. and Stille, J. K., Tetrahedron Lett., 23, 627 (1982). 79 Widdowson, D. A., Wiebecke, G. H., and Williams, D. J., Tetrahedron Lett., 23,4285 (1982).

Girnth-Weller, M., and Beck, W., Inorg. Chim. Acta., 57, 107 (1982). Quast, H., Miller, B., Peters, K., and Schnering, H. G. von, Chem. Ber., 115, 1525 (1982). (a) Sakai, T., Ishizaki, M., and Goto, M., Bull. Chem. SOC. Jpn., 55,2409 (1982); (b)Matsumoto, T., and Inone, S., J. Chem. SOC., Perkin Trans. I , 1982, 1975.

83 Wesdemiotis, C., and McLalTerty, F. W., Org. Mass Spectrom., 16,381 (1981); Chem. Abs., 96,103326 (1982).

84 Ritchie, C. D., VanVerth, J. E., and Virtanen, P. 0. I., J. A m Chem. SOC., 104, 3491 (1982). ” Pocker, Y., Meany, J. E., and Jones, R. C., J . A m Chem. SOC., 104, 4885 (1982).

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143 (1982); Chem. Abs., 97, 5722 (1982).

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SSSR, Ser. Khim., 1982; 1359; Chem. Abs., 97, 91361 (1982). Stanczyk, W., Chmielecka, J., and Chojnowski, J., J . Org. Chem., 47, 3757 (1982). Ananthakrishnanadar, P., and Kannan, N., Indian J . Chem., 21A, 74 (1982); Chem Abs., %, 216927 (1982).

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93 Soai, K., Komiya, K., Shigematsy Y., Hasegawa, H., and Ookawa, A., J. Chem. SOC., Chem. Commun.,

94 Midland, M. M., and Zderic, S. A,, J. Am. Chem. SOC., 104, 525 (1982). ” Craze, G.-A,, and Watt, I., Tetrahedron Lett., 23, 975 (1982). 96 Lemikre, G. L., Van Osselaer, T. A,, Lepoivre, J. A., and Alderweireldt, F. C., J . Chem. SOC., Perkin

97 Ingemann, S., Kleingeld, J. C., and Nibbering, N. M. M., J . Chem. SOC., Chem. Commun., 1982,1009. ’’ Kwart, H., and Brechbiel, M. W., J. Org. Chem., 47, 3353 (1982). ’’ Cavazza, M., Morganti, G., Veracini, C. A., Guerriero, A., and Pietra, F., Tetrahedron Lett., 23,4115

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16 102

103

104

105

106

107

108

I09

110

1 1 1

112

113

114

115

116

117

118

Organic Reaction Mechanisms 1982

Gambaro, A., Ganis, P., Marton, D., Peruzzo, V., and Tagliavini, F., J. Organomet. Chem., 231,307 (1982). Lasperas, M., Perez-Ossorio, R., Peez-Rubalcaba, A., and Quiroga-Feijoo, M. L., An. Quim., 77C, 112 (1981); Chem. Abs., 97, 54944 (1982). Alvarez-Ibarra, C., Arias, P. M. S., Garcia-Romo, M. T., and Perrez-Ossorio, R., An. Quim., 77C, 40 (1981); Chem. Abs., 97,71672 (1982). Benkeser, R. A., and Snyder, D. C., J. Org. Chem., 47, 1243 (1982). Bernadon, C., and Deberly, A., J. Org. Chem., 47,463 (1982). Guerriero, A., Pietra, F., Cavazza, M., and Del Cima, F., J. Chem. Soc., Perkin Trans. 1,1982,979. Kulinkovich, 0. G., Tischenko, I. G., and Danilovich, S. V., Zh. Org. Khim., 17,1196 (1981); Chem. Abs., 95,203173 (1981). Hayashi, T., Konishi, M., and Kumada, M., J. A m Chem. Soc., 104,4963 (1982). Arjona, O., Perez-Ossorio, R., Perez-Rubalcaba, A., and Quiroga, M. L., J. Chem. Soc., Chem. Commun., 1982, 452. Hoffmann, R. W., Angew. Chem. Int. Ed., 21, 555 (1982). Dehmlow, E. V., and Shamout, A. R., Liebigs Ann. Chem., 1982, 1750. Lee, I., and Yang, K., Bull. Korean Chem. Soc., 2, 132 (1981); Chem Abs., 96, 103297 (1982). Toullec, J., Adv. Phys. Org. Chem., 18, 1 (1982). Albery, W. J., and Gelles, J. S., .I. Chem. Soc., Faraday Ttans. I , 78, 1569 (1982). Albery, W. J., J. Chem. SOC., Faraday Ttans. 1,78, 1579 (1982). Johnson, D. M., J. Org. Chem., 47, 198 (1982). Okuvama T.. Kimura K., and Fueno, T., Bull. Chem SOC. Jpn., 55, 1493 (1982).

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organic reaction mechanisms 1982...organic reaction mechanisms 1982 an annual survey covering the...

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