Abstract
The main strategies for the ring opening of β-lactams by chemical means are described. The discovery of each approach is put into context, sometimes in connection to processes occurring in biological systems, and the synthetic opportunities each approach offers are shown. Thus, this β-lactam route affords a number of synthetically relevant building-blocks, including α-amino acids, β-amino acids, their derived peptides, and other nitrogen containing heterocycles and open chain molecules. The content, which encompases references to initial work, further major development, and the most relevant recent literature contributions, is categorized according to the ring bond cleavaged (N 1–C 2, C 2–C 3, C 3 –C 4 , N 1–C 4), to finish with ring opening strategies leading to large heterocyclic compounds. Within each category, distinction has been made according to the type of nucleophilic agent employed, principally O-, N-, and C-nucleophiles. Also, a variety of applications of the strategy to the synthesis of interesting target compounds are shown.
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Abbreviations
- Ac:
-
Acetyl
- AcOH:
-
Acetic acid
- AD:
-
Asymmetric dihydroxylation
- Ar:
-
Aryl
- Bn:
-
Benzyl
- Boc:
-
tert-butoxycarbonyl
- Bu:
-
Butyl
- Bz:
-
Benzoyl
- CAN:
-
Ceric ammonium nitrate
- Cbz:
-
Benzyloxycarbonyl
- cHex:
-
Cyclohexyl
- CSA:
-
Camphorsulfonic acid
- DCC:
-
N,N-dicyclohexylcarbodiimide
- DIBAL:
-
Lithium diisobutylaluminium hydride
- DMAP:
-
4-(dimethylamino)pyridine
- DMD:
-
Dimethyldioxirane
- DMF:
-
Dimethylformamide
- DMSO:
-
Dimethyl sulfoxide
- Et:
-
Ethyl
- Fmoc:
-
9-fluorenylmethoxycarbonyl
- Gly:
-
Glycine (glycinyl)
- HMDS:
-
Hexamethyldisilazide
- HMPA:
-
Hexamethylphosphoric triamide
- HOBt:
-
N-hydroxyl benzotriazole
- LDA:
-
Lithium diisopropylamide
- Leu:
-
Leucine (leucinyl)
- LHMDS:
-
Lithium hexamethyldisilazide
- mCPBA:
-
3-chloroperoxybenzoic acid
- Me:
-
Methyl
- MS:
-
Molecular sieves
- NCA:
-
N-carboxy anhydride
- NDC:
-
Nicotinium dichromate
- NMM:
-
N-methyl morpholine
- Nu:
-
Nucleophile
- PDC:
-
Pyridinium dichromate
- Ph:
-
Phenyl
- Phe:
-
Phenylalanine (phenylalaninyl)
- PMP:
-
4-(methoxy)phenyl
- Pr:
-
Propyl
- p-Tos:
-
4-(methylphenyl)sulfonyl
- p-Tolyl:
-
4-methylphenyl
- SEM:
-
2-(trimethylsilyl)ethoxymethyl
- Succ:
-
Succinyl
- TBAF:
-
Tetrabutylammonium fluoride
- TBDPS:
-
tert-butyldiphenylsilyl
- TBS:
-
tert-butyldimethylsilyl
- TEMPO:
-
2,2,6,6-tetramethylpiperidinyl-1-oxyl
- TES:
-
Triethylsilyl
- TFA:
-
Trifluoroacetic acid
- THF:
-
Tetrahydrofuran
- Thz:
-
2-thiazolyl
- TIPS:
-
Triisopropylsilyl
- TMS:
-
Trimethylsilyl
- TMSOTf:
-
Trimethylsilyl trifluoromethanesulfonate
- UV:
-
Ultraviolet
- Val:
-
Valine (valinyl)
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Acknowledgements
We thank the following institutions for financial support of our β-lactam program: Ministerio de Educación y Ciencia (Spanish Government), Eusko Jaurlaritza (Basque Government), Euskal Herriko Unibertsitatea-Universidad del País Vasco (University of the Basque Country), and Diputación Foral de Gipuzkoa. All team members cited within the references are also acknowledged.
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Palomo, C., Oiarbide, M. (2010). β-Lactam Ring Opening: A Useful Entry to Amino Acids and Relevant Nitrogen-Containing Compounds. In: Banik, B. (eds) Heterocyclic Scaffolds I. Topics in Heterocyclic Chemistry, vol 22. Springer, Berlin, Heidelberg. https://doi.org/10.1007/7081_2009_11
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