Modifications on the basic skeletons of vinblastine and vincristine - PubMed (original) (raw)

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Modifications on the basic skeletons of vinblastine and vincristine

Péter Keglevich et al. Molecules. 2012.

Abstract

The synthetic investigation of biologically active natural compounds serves two main purposes: (i) the total synthesis of alkaloids and their analogues; (ii) modification of the structures for producing more selective, more effective, or less toxic derivatives. In the chemistry of dimeric Vinca alkaloids enormous efforts have been directed towards synthesizing new derivatives of the antitumor agents vinblastine and vincristine so as to obtain novel compounds with improved therapeutic properties.

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Figures

Figure 1

Figure 1

Structures of vinblastine (1) and vincristine (2).

Scheme 1

Scheme 1

Preparation of 17-desacetylvinblastine-16-amide (5).

Scheme 2

Scheme 2

Selective desacetylation of vinblastine (1).

Scheme 3

Scheme 3

Amino acid derivatives of vinblastine.

Scheme 4

Scheme 4

Hydrazide derivatives 8 and 9 of vinblastine (1).

Scheme 5

Scheme 5

Iodination reactions on vinblastine (1).

Scheme 6

Scheme 6

Bromination and formylation of vinblastine (1).

Scheme 7

Scheme 7

Reactions of 12′-iodovinblastine (10).

Scheme 8

Scheme 8

Reduction of vinblastine (1).

Scheme 9

Scheme 9

Fluorination reaction of vinblastine (1).

Scheme 10

Scheme 10

Nitration of vinblastine (1).

Scheme 11

Scheme 11

Coupling of vinblastine (1) with amino acids.

Scheme 12

Scheme 12

Vinblastine derivatives conjugated with carrier peptide.

Scheme 13

Scheme 13

Synthesis of vinorelbine (33).

Scheme 14

Scheme 14

Oxidation of vinblastine (1) to vincristine (2).

Scheme 15

Scheme 15

Ring transformation reaction.

Scheme 16

Scheme 16

Preparation of vinamidine (35).

Scheme 17

Scheme 17

Spiro-substituted dimer alkaloids.

Scheme 18

Scheme 18

Deacetylation of vincristine (2).

Scheme 19

Scheme 19

Reduction of vincristine (2).

Scheme 20

Scheme 20

Nitration of vincristine (2).

Scheme 21

Scheme 21

Iodinated derivatives of vincristine (2).

Scheme 22

Scheme 22

Selective deacetylation of vincristine (2).

Scheme 23

Scheme 23

Detailed synthesis of vinflunine (58).

Scheme 24

Scheme 24

Preparation and reaction of 9-chlorocatharanthine (59).

Scheme 25

Scheme 25

Building in an oxirane ring to catharanthine (3).

Scheme 26

Scheme 26

Preparation of leurosidine (65).

Scheme 27

Scheme 27

New derivatives of catharanthine.

Scheme 28

Scheme 28

Fluoro-substituted dimeric alkaloids.

Scheme 29

Scheme 29

Coupling with saturated vindoline.

Scheme 30

Scheme 30

Carbamates of vinblastine.

Scheme 31

Scheme 31

Amide substitued anhydrovinblastine derivatives.

Scheme 32

Scheme 32

Modification of C-20 ethyl substitutent of vindoline.

Scheme 33

Scheme 33

Vinblastines substituted at the vindoline D-ring.

Scheme 34

Scheme 34

Coupling vindoline (4) with substituted catharanthines.

Scheme 35

Scheme 35

Coupling in a one-step reaction.

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References

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