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112 Chemistry and Biology of Beta-Lactams
O
Ph
O
Ph
HO
OH
R
HO
OAc
OAc
RuCl
,
NaIO
https://t.me/med1917
Ph H
N
O
O
R
+
H
O
N
N
R
Cu source, Ligand
Ph
Me
R
Base
Me
Me
Me
Me
Me
Fe
N
N
R
Me
Me
Me
Fe
Me
Me
SCHEME 3.96 Synthesis of β-Lactams Using Metal-mediated Reactions.
O
TMSCl
O
OH
OO
NaH
O
I
OH
Major
OO
O
N
PhPh
+
N
PhPh
Minor
N
N
O
O
N
O
NaOH
O
OO
O
OH
RNH
NaIO
4
OO
CHO
O
M
gSO
2
4
OO
H
O
N
1
SCHEME 3.97 Synthesis of β-Lactams Using Isosorbide.
H
O
O
H
R
triphosgene,
OH
1
N
AcOH
DMAP/DCC
2
R
N
Et
3
HO
R
O
major
1
N
O
H
H
R
O
OAc
(60%)
2
H
H
O
Allyl
H
O
H
O
bromide
1
R
N
+
2
R
H
O
SCHEME 3.98 Chiral Synthesis of β-Lactams Using Isosorbide.
OO
2
R
CH
COCl,
2
O
O
H
O
H
O
O
H
OAc
N
Et
3
3
O
OAc
CH
H
CN,
3
O
2
H
H
O
CCl
H H
2
R
N
1
R
O
4
4
O
OH
H
O
O
H
O
OH
H
O OAc
H
R
1
2
1
2
Me
O
1
2
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O
Br
H
Acetyl Chloride
N
Et
3
Jones
oxidation.
N
H
1
R
H
H
H
Zn/AcOH
NBS/ethelene glycol
N
O OH
H
1
R
H
H
SCHEME 3.99 Synthesis of Polyaromatic β-Lactams Using Carene.
113Polycyclic Beta-Lactams
N
2
Et
DCM
N,
3
Mukaiyama
R
reagent
N
O O
H
1
R
H
H
Br
H
O
OH
O
Br
H
HH
N R
N
O
H
R
HH
N R
1
+
R
O
1
N
Bi(NO3)
R
2
O
3
O
1
N
Bi(NO3)
R
2
3
HH
N R
N
O
1
+
R
2
HH
N R
N
O
R
SCHEME 3.100 Synthesis of Pyrrole-Substituted-β-Lactams.
Me
O
S
O
HH
2
R
O
3
N
O
O
S
O
HH
O
3
N
O
1
R
2
R
1
R
AcONa, DMSO
Ultrasound
AcONa, DMSO
Ultrasound
Me
Me
OHHC
O
O
OHHC
O
2
R
3
N
R
1
R
3
N
R
SCHEME 3.101 Ultrasound-Induced Synthesis of Trans-β-Lactams By Inversion of Conguration.
A chiral acid obtained from (+)-car-3-ene was employed. (+)-Car-3-ene on bromination with NBS
gave bromoalcohol. Jones oxidation of bromoalcohol was conducted to obtain bicyclic chiral acid. The
cycloaddition of bicyclic acid with imines in the presence of Mukaiyama reagent was conducted to yield
trans-β-lactams. The auxiliary was removed by Zn/AcOH. An acetylation gave trans-β-lactams (Scheme
3.99). The cycloaddition was also possible under microwave condition.
The reaction of racemic α-keto-β-lactams with trans-4-hydroxy L-proline and cis-4-hydroxy D-proline
160
in the presence of bismuth nitrate gave a diastereomeric mixture of β-lactams with a pyrrole ring. Several
green syntheses
Four diastereomers were produced with a high degree of cis-diastereoselectivity. This was the rst
report of enantiomerically pure pyrrole-substituted β-lactams (Scheme 3.100). This method was also
161–165
including catalytic reactions were conducted in our lab.
166 –171
conducted using microwave-mediated reaction. We have investigated microwave-induced reactions
extensively.
Banik et al.
172 –189
190
demonstrated an ultrasound-induced asymmetric preparation of trans-acetoxy β-
lactams. A nucleophilic reaction of cis-3-mesyl β-lactams with sodium acetate afforded trans-3-acetoxy
β-lactams under this condition (Scheme 3.101).
114 Chemistry and Biology of Beta-Lactams
O
tBu
R
O
2
R
O
O
Ar
Ar
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S
HN
tBu
1
2
R
R
O
O
N
2
HCl
NH
1
R
O
O
O
R
tBu
SCHEME 3.102 Synthesis of β-Lactams Related to Monobactams.
1
R
O
N
OMe
CAN
H
2
R
O,
1
PS
R
NH
Lipase
COOH
2
1
R
R
O
NH
O
HN
+
1
R
R
MeOH, PS Lipase
SCHEME 3.103 Chemoenzymatic Synthesis of β-Lactams.
O
H
O
PMP
Allylbromide
Zn
O
N
O
O
OH
N
PMP
O
O
Allylbromide
TBAI
2
R
2
O
LiHMDS
O
N
PMP
OH
R
1
R
N
H
O
1
R
R
O
O
[Cl
(PCy3)
2
CO
2
NH
2
Ru=CHPh
2
Me
+
]
1
R
R
O
HN
O
O
O
N
PMP
O
THF/H
2h
,
4
H
N
NaHCO
O
Ar
O
(1:1),
2
3
1-bromo-2-butyne,
O
In,
PTSA,
reflux,
NaIO
O
O
SCHEME 3.104 Synthesis of Spirocyclic β-Lactams by Zinc.
Guerrini et al.
group. A LiHMDS-mediated cyclization of the freebase produced 3-substituted-3-hydroxy-β-lactam. Th is
β-lactam is a crucial precursor for the preparation of monobactams (sulfazecin) and an enzyme inhibitor
(tabtoxin). The C4 conguration of the β-lactam was identical with that of the C1-aminodioxolanones
(Scheme 3.102).
A chemoenzymatic enantiospecic synthesis of β-lactams was reported by Kanerva et al.
cally active uorinated β-lactams demonstrated a signicant impact on medicines. The PS lipase in
methanol and in water was able to form the products (Scheme 3.103).
Benito et al.
193
spiro molecules were made using metal-induced carbonyl addition/cyclization reactions. Substituted
O
CHO
N
PMP
O
H
Cl
THF/N
4
191
reported the preparation of a chiral base via deprotection of N-tert-butylsulnylamino
O
OH
O
AgNO
3
N
PMP
O
OH
H
O
OH
NaIO
N
O
4
CHO
N
192
The opti-
developed a convenient procedure for the synthesis of spirocyclic β-lactams. These
SCHEME 3.105 Diastereoselective Synthesis of Bicyclic β-Lactams.
O
O CO
Me
Me
Ph
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115Polycyclic Beta-Lactams
2
N
CO
2
Me
2
N
Me
CO
2
Ar
Me
CO
2
C
alkyl
+
MeO2C
O
C
+
Et
MeO2C
N
Me
CO
2
N
5%
5%
(-)-A
(-)-A
Ar
alkyl
O CO
Ph
Et
N
Fe
R
1
R
A
Me
(-)-
B
Ph
SCHEME 3.106 Nucleophilic Catalysis Process for the Synthesis of β-Lactams.
(-)-
1
R
1
R
1
R
1
alkoxy-β-lactam aldehydes through a four-step reaction involving zinc-induced allylation, cyclization,
and oxidative cleavage afforded the desired spirocyclic β-lactams (Scheme 3.104).
A diastereoselective preparation of bicyclic β-lactams via an annulation reaction of 3-alkyl or 3-aryl
enals and chalcone-derived imines was demonstrated by Bode et al.
194
The NHC-mediated reactions of
enals and α,β-unsaturated ketones produced cyclopentenes through a cascade reaction like a crossedbenzoin/oxy-Cope rearrangement. In principle, β-lactone or β-lactam products were possible (Scheme
3.105).
β-lactams was reported by Fu et al.
β-lactams. No papers on nucleophilic catalysis of cycloaddition between ketene and azo compounds
were known. The pyrrolidino derivative induced the catalytic asymmetric preparation of aza-β-lactams
(Scheme 3.106).
Muñiz et al.
β-lactam. Resin-bound amino acids were employed for solid-phase synthesis of this type of β-lactams.
195
Catalytic reaction of ketenes with imines gave optically active
196
showed a four-step method for the solid-phase synthesis of chiral tetrasubstituted
116 Chemistry and Biology of Beta-Lactams
H
H
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SCHEME 3.107 Chiral Synthesis of β-Lactams Using Solid-Phase Method.
SCHEME 3.108 Photochemical Synthesis of Chiral β-Lactams.
ClO2S
N
ClO2S
O
H
H
O
N
H
H
CSI
H
O
ClO2S
H
SO2Cl
N
N
H
H
N
SO
2
SO
O
3
H
H
O
HN
3
H
Na
2
H
O
Na
H
SCHEME 3.109 Synthesis of Tricyclic β-Lactams from Carene.
Numerous chiral quaternary cis-β-lactams were prepared using this procedure. The cyclization of chiral
N-2-chloroalkanoylamino acid was important to generate the chirality (Scheme 3.107).
Fujita et al.
197
demonstrated the preparation of a chiral β-lactam by photochemical γ-hydrogen abstraction of thioimide. The photochemical method demonstrated γ-hydrogen abstraction of monothioimides.
The reaction took place through a diradical intermediate. A number of chiral β-lactams were prepared
using this method (Scheme 3.108).
The preparation of tricyclic β-lactams by reaction of chiral car-2-ene and chlorosulfonyl isocyanate
was reported by Koneva et al.
198
The sulfuryl chloride isocyanate (ClSO2NCO) was able to form two
carbocations. These tertiary carbocations formed a bond with nucleophilic nitrogen to obtain tricyclic
β-lactams. The β-lactam ring and the cyclopropane ring became trans to each other (Scheme 3.109).
Ando et al.
199
demonstrated the synthesis of (S)-diuoro-β-lactams (Scheme 3.110).
Bromodiuoroacetates on reaction with chiral alcohols gave chiral esters. The ester on rhodium metalinduced Reformatsky reaction with Schiff base produced diuoro-β-lactams.
Otani et al.
200
investigated the preparation of chiral trans- and cis-β-lactams using metal ligand. The
C2-symmetric bis-(oxazoline) ligand was a good source for the Kinugasa reaction. The formation of the
cis-isomer was higher than that of the trans-product (Sch e me 3.111).
Vassilev et al.
201
developed a method in which formation of chiral trans-β-lactam was only seen.
Microwave-induced irradiation of an optically pure amine and racemic aldehyde was performed. The
imine on cycloaddition produced trans-β-lactam (Scheme 3.112).
117Polycyclic Beta-Lactams
Br
PMB
2
FF
*
Ph
PhPh
RN
*
R
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RhCl(PPh3)
Et
O
2
NH
O
Zn
N
HPh
N
PMB
,
3
Ph
PhPh
+
R
N
O
O
O
FF
SCHEME 3.110 Synthesis of Optically Active β-Lactams by Reformatsky Reaction.
+
Ph
+
Chiral
KOt-Bu
O
O
alcohol
N
N
Br
R
FF
Cu(OTf)
S
O
O
-
Bu
O
NH
2
Cu(OTf)
H
N
R
*
2
-
Bu
S
2
H
N
PMB
O
N
PhPh
+
F
F
N
O
+
NH
O
Ph
R
PhPh
N
O
R
O
SCHEME 3.111 Stereocontrolled Synthesis of β-Lactams Using metal Ligand.
SCHEME 3.112 Stereospecic Synthesis of β-Lactams by Microwave.
Garud et al.
202
with optically active 4-acetoxyazetidinone and selenating substrate afforded trans-β-lactam. The anion
produced on nitrogen by base treatment following kinetic and thermodynamics condition yielded transβ-lactam (Scheme 3.113).
Rosa et al.
203
imine. A mixture of the two spiro-β-lactams was isolated. Spiro-β-lactams showed a cis-stereochemistry
between N-Cbz and phenyl groups (Scheme 3.114).
Smith et al.
204
and imines to obtain β-lactams. The NHC derived from the C2-symmetric imidazolinium salts helped
β-lactam formation from a ketene and a range of imines (Scheme 3.115).
A catalytic Lewis base-induced cycloaddition of ketenes was developed by Smith et al.
dition of ethylphenylketene with Schiff bases was investigated. The preparation of β-lactam from diphenylketene and N-tosyl imine was successful (Scheme 3.116).
Rimoldi et al.
yeasts. The phenylpropanoate was converted into phenyl-substituted azetidinones through ester hydrolysis and cyclization of the amino acid (Scheme 3.117).
R
H
2
MW
O
*
N
R
PhCH
R
PhCH
2CH2
2CH2
COCl
COCl
O
N
*
R
Ph
introduced alkene-seleno groups at the C4 position of the β-lactams. The reaction
explored the preparation of spiro-β-lactams by reacting proline carboxylic acid and
explored catalytic Lewis base-induced reaction for asymmetric cycloaddition of ketenes
205
A cycload-
206
prepared optically active β-lactam via catalytic asymmetric/biotransformation using
118 Chemistry and Biology of Beta-Lactams
OSBT
O
MsO
O
MeOH
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H H
O
RBr,
SeK
NaH
RBr,
Me
DMF
OSBT
H H
Se
N
R
O
Se
n
SCHEME 3.113 Synthesis of β-Lactams Containing Selenium.
N
Cl
I
Me
PhCH=NBn
O
N
Et
N
OH
R
3
MsO
N
R
Ph
O
Me
n
Cs2CO
MeNHNH
+
N
Bn
O
3
MsO
NH
2
OAc
N
R
Me
O
Ph
OSBT
H H
O
N Bn
NH
Se
n
K
CO
,
2
K
MeOH
CO
,
2
3
Ph
+
N
N
R
Bn
N
R
3
O
N Bn
Ph
SCHEME 3.114 Synthesis of Spirocyclic β-Lactams.
Herdewijn et al.
207
prepared β-lactam with lipopeptides. These molecules act as initial point to study
the reactivity of the β-lactam in peptidomimetics. The phthalimido-protected compound was reduced
to amino acid. The phthalimido amino acid was then cyclized to prepare phthalisoimides. The phthalisoimide cis-compound was hydrogenated to obtain the amine intermediate. The coupling reaction of
amine with the decanoyl-PTAN-COOH produced four lipopeptides (Scheme 3.118).
Long et al.
208
explored a process to prepare cis-β-lactams using photochemistry. The photooxida-
tion of thiazolidines was performed with singlet oxygen. It was produced from triplet O2 via 500 W
halogen lamp with a photosensitizer, tetraphenylporphyrin (TTP). Mesylation and cyclization produced
N-substituted monocyclic cis-β-lactams (Scheme 3.119).
Bull et al.
clic β-lactams. These polycyclic β-lactams were used for the preparation of β-amino acids. Lithium or
potassium enolates of a precursor underwent cyclization to generate a mixture of β-lactams in moderate
209
used an intramolecular ester enolate-imine cyclization for the preparation of polycy-
yields. Finally, clean formation of tricyclic β-lactam was achieved (Scheme 3.120).
3.4 Conclusion
Because of their medicinal properties and uses as starting compounds, diverse synthesis and biological investigations of β-lactams have been conducted extensively for the past many decades. Since the
119Polycyclic Beta-Lactams
Ph
Ph
Ph
Ph
Br
Br
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SCHEME 3.115 Lewis-Base-Induced Catalytic Synthesis of β-Lactams.
BF4
N
N
KHDMS
O
SCHEME 3.116 Lewis Base-Induced Synthesis of β-Lactams.
Ts
N
H
Ph
Ph
Ts
O
N
preparation of penicillin, new families of β-lactam antibiotics have received attention. This series of
compounds have wide applications in many other medical disorders. Asymmetric synthesis of β-lactams
has been investigated by a number of research groups. Many crucial strategies have been discovered
for the synthesis of the 2-azetidinone system present in β-lactams. These include Staudinger cycloaddition, enolate-imine condensation, hydroxamate reaction, alkene-isocyanate reaction, and alkyne-nitrone
method. Some of these methods have demonstrated excellent enantio- and diastereoselectivity. Domestic
microwave-induced reactions have dramatic effects on the stereochemistry and rate of the β-lactam
formation. Many β -lactams are used for the preparation of other heterocyclic compounds of medicinal
signicance. The research scope on β -lactams has remained highly signicant. Therefore, we expect to
nd numerous notable discoveries based upon this subject in the coming years.
120 Chemistry and Biology of Beta-Lactams
Ph
OOH
NH
OH
O
O
n
R
OR
PMP
t
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OOH
OEt
NHCOPh
10%
Et
Ph
N
3
OH
NHCOPh
PPh
HCl
Br
Ph
OH
H
Br
N
Br
NaH
SCHEME 3.117 Synthesis of Optically Active β-Lactams by Catalytic Method.
O
N
O
O
N-methylhydrazine
S
OBn
N
O
H2N
·
Na
S
2
S
OBn
N
O
O
O
S
HN
N
OH
O
O
Dec-PTAN-COOH
EDCI
HOBt,
O
OBn
H3C(H2C)
DCC
DCM
8
O
N
,
PySSPy
3
O
HO
H
Ph
O
S
N
O
O
O
H
N
N
H
O
NH
OBn
N
O
O
NH
S
N
2
O
OB
SCHEME 3.118 Synthesis of β-Lactams With Lipopeotides.
O
O
N
RON
O
S
NHOR'
hv,
TPP,
MsCl
THF
O
R
H
O
O
,
2
S
OH
O
R
N
S
O
O
NHOH'
N
S
H
N
SCHEME 3.119 Photo-catalyzed Synthesis of β-Lactams.
N
OEt
H
n
O
NaHMDS
15-crown-5
PMP
O
N
SCHEME 3.120 Intermolecular Ester-Enolate Reaction Toward β-Lactams.
Rearrangement
PMP
+
N
O
R
O
O
+
N
NHOR'
PMP
S
OOH
NH
COOE
121Polycyclic Beta-Lactams
https://t.me/med1917
Acknowledgements
AD is grateful to CEA-Grenoble, Joseph Fourier University, University of Göttingen, and University of
Californ ia, Los Angeles for their support. BKB is grateful to US NIH, US NCI, Texas Kleberg Foundation,
Stevens Institute of Technology, University of Texas M. D. Anderson Cancer Center, University of TexasPan American, University of Texas Health Science Center-San Antonio and Community Health Systems
of Texas for their competitive nancial and moral support to his research. AD and BKB acknowledges
support from their current employer, Prince Mohammad Bin Fahd University. The authors are grateful
to Dr. Aarif Shaikh for his contributions and useful discussions.
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