Combining enyne metathesis with long-established organic transformations: a powerful strategy for the sustainable synthesis of bioactive molecules
- Valerian Dragutan,
- Ileana Dragutan,
- Albert Demonceau and
- Lionel Delaude
Beilstein J. Org. Chem. 2020, 16, 738–755, doi:10.3762/bjoc.16.68
Graphical Abstract
Scheme 1: Intramolecular (A) and intermolecular (B) enyne metathesis reactions.
Scheme 2: Ene–yne and yne–ene mechanisms for intramolecular enyne metathesis reactions.
Scheme 3: Metallacarbene mechanism in intermolecular enyne metathesis.
Scheme 4: The Oguri strategy for accessing artemisinin analogs 1a–c through enyne metathesis.
Scheme 5: Access to the tetracyclic core of nanolobatolide (2) via tandem enyne metathesis followed by an Eu(...
Scheme 6: Synthesis of (−)-amphidinolide E (3) using an intermolecular enyne metathesis as the key step.
Scheme 7: Synthesis of amphidinolide K (4) by an enyne metathesis route.
Scheme 8: Trost synthesis of des-epoxy-amphidinolide N (5) [72].
Scheme 9: Enyne metathesis between the propargylic derivative and the allylic alcohol in the synthesis of the...
Scheme 10: Synthetic route to amphidinolide N (6a).
Scheme 11: Synthesis of the stereoisomeric precursors of amphidinolide V (7a and 7b) through alkyne ring-closi...
Scheme 12: Synthesis of the anthramycin precursor 8 from ʟ-methionine by a tandem enyne metathesis–cross metat...
Scheme 13: Synthesis of (−)‐clavukerin A (9) and (−)‐isoclavukerin A (10) by an enyne metathesis route startin...
Scheme 14: Synthesis of (−)-isoguaiene (11) through an enyne metathesis as the key step.
Scheme 15: Synthesis of erogorgiaene (12) by a tandem enyne metathesis/cross metathesis sequence using the sec...
Scheme 16: Synthesis of (−)-galanthamine (13) from isovanilin by an enyne metathesis.
Scheme 17: Application of enyne metathesis for the synthesis of kempene diterpenes 14a–c.
Scheme 18: Synthesis of the alkaloid (+)-lycoflexine (15) through enyne metathesis.
Scheme 19: Synthesis of the AB subunits of manzamine A (16a) and E (16b) by enyne metathesis.
Scheme 20: Jung's synthesis of rhodexin A (17) by enyne metathesis/cross metathesis reactions.
Scheme 21: Total synthesis of (−)-flueggine A (18) and (+)-virosaine B (19) from Weinreb amide by enyne metath...
Scheme 22: Access to virgidivarine (20) and virgiboidine (21) by an enyne metathesis route.
Scheme 23: Enyne metathesis approach to (−)-zenkequinone B (22).
Scheme 24: Access to C-aryl glycoside 23 by an intermolecular enyne metathesis/Diels–Alder cycloaddition.
Scheme 25: Synthesis of spiro-C-aryl glycoside 24 by a tandem intramolecular enyne metathesis/Diels–Alder reac...
Scheme 26: Pathways to (−)-exiguolide (25) by Trost’s Ru-catalyzed enyne cross-coupling and cross-metathesis [94].
Recent advances in metathesis-derived polymers containing transition metals in the side chain
- Ileana Dragutan,
- Valerian Dragutan,
- Bogdan C. Simionescu,
- Albert Demonceau and
- Helmut Fischer
Beilstein J. Org. Chem. 2015, 11, 2747–2762, doi:10.3762/bjoc.11.296
Graphical Abstract
Scheme 1: Synthesis of homopolymers containing ferrocenyl and tetraethylene glycol groups.
Scheme 2: Synthesis of redox-robust triazolylbiferrocenyl polymers 4.
Scheme 3: Synthesis of cobaltocenium-containing polymers by ROMP.
Scheme 4: Cobaltocenium-appending copolymers by the ROMP approach (X = PF6, Y = BPh4 or Cl).
Scheme 5: Cobalt-containing polymers by click and ROMP approach.
Scheme 6: Synthesis of new cobalt-integrating block copolymers.
Scheme 7: Two alternative routes for the synthesis of redox-active cobalticenium-tethered polyelectrolytes.
Scheme 8: Oxanorbornene monomers for the synthesis of Ru-containing polymers by ROMP.
Scheme 9: ROMP synthesis of Ru-containing homopolymers.
Scheme 10: Synthesis of diblock copolymers incorporating ruthenium.
Scheme 11: Synthesis of Ru triblock copolymers.
Scheme 12: Synthesis of cross-linked Ru-containing triblock copolymers.
Scheme 13: Synthesis of Ir-containing homopolymers by ROMP.
Scheme 14: Monomers for Ir- and Os-containing ROMP polymers.
Scheme 15: ROMP block copolymers integrating Ir in their side chains.
Scheme 16: Synthesis of Rh-containing block copolymers.
Scheme 17: Access to rhodocenium-containing metallopolymers by ROMP.
Scheme 18: Synthesis of homopolymers equipped with Cu coordination centers.
Scheme 19: Synthesis of Cu-containing copolymers (spacer = –(CH2)5–; >C=O).
Scheme 20: Synthesis of polynorbornene bearing a polyoxometalate (POM) cluster in the side chain.
Scheme 21: Synthesis of Eu-containing copolymers by a ROMP-based route.
Metathesis access to monocyclic iminocyclitol-based therapeutic agents
- Ileana Dragutan,
- Valerian Dragutan,
- Carmen Mitan,
- Hermanus C.M. Vosloo,
- Lionel Delaude and
- Albert Demonceau
Beilstein J. Org. Chem. 2011, 7, 699–716, doi:10.3762/bjoc.7.81
Graphical Abstract
Scheme 1: Well-defined Mo- and Ru-alkylidene metathesis catalysts.
Scheme 2: Representative pyrrolidine-based iminocyclitols.
Scheme 3: Synthesis of (±)-(2R*,3R*,4S*)-2-hydroxymethylpyrrolidin-3,4-diol (18), (±)-2-hydroxymethylpyrrolid...
Scheme 4: Synthesis of enantiopure iminocyclitol (−)-(2S,3R,4S,5S)-2,5-dihydroxymethylpyrrolidin-3,4-diol (23...
Scheme 5: Synthesis of 1,4-dideoxy-1,4-imino-D-allitol (29) and formal synthesis of (2S,3R,4S)-3,4-dihydroxyp...
Scheme 6: Synthesis of iminocyclitols 35 and 36.
Scheme 7: Total synthesis of iminocyclitols 40 and 44.
Scheme 8: Synthesis of 2,5-dideoxy-2,5-imino-D-mannitol [(+)-DMDP] (49) and (−)-bulgecinine (50).
Scheme 9: Synthesis of (+)-broussonetine G (53).
Scheme 10: Structural features of broussonetines 54.
Scheme 11: Synthesis of broussonetines by cross-metathesis.
Scheme 12: Representative piperidine-based iminocyclitols.
Scheme 13: Total synthesis of 1-deoxynojirimycin (62) and 1-deoxyaltronojirimycin (65).
Scheme 14: Synthesis by RCM of 1-deoxymannonojirimycin (63) and 1-deoxyallonojirimycin (66).
Scheme 15: Total synthesis of (+)-1-deoxynojirimycin (62).
Scheme 16: Synthesis of ent-1,6-dideoxynojirimycin (83) and 5-amino-1,5,6-trideoxyaltrose (84).
Scheme 17: Synthesis of 1-deoxygalactonojirimycin (64), 1-deoxygulonojirimycin (91) and 1-deoxyidonojirimycin (...
Scheme 18: Synthesis of L-1-deoxyaltronojirimycin (96).
Scheme 19: Synthesis of 1-deoxymannonojirimycin (63) and 1-deoxyaltronojirimycin (65).
Scheme 20: Synthesis of 5-des(hydroxymethyl)-1-deoxymannonojirimycin (111) and 5-des(hydroxymethyl)-1-deoxynoj...
Scheme 21: Synthesis of D-1-deoxygulonojirimycin (91) and L-1-deoxyallonojirimycin (122).
Scheme 22: Total synthesis of fagomine (129), 3-epi-fagomine (126) and 3,4-di-epi-fagomine (130).
Scheme 23: Total synthesis of (+)-adenophorine (135).
Scheme 24: Total synthesis of (+)-5-deoxyadenophorine (138) and analogues 142–145.
Scheme 25: Synthesis by RCM of 1,6-dideoxy-1,6-iminoheptitols 148 and 149.
Scheme 26: Synthesis by RCM of oxazolidinyl azacycles 152 and 154.
Scheme 27: Representative azepane-based iminocyclitols.
Scheme 28: Synthesis of hydroxymethyl-1-(4-methylphenylsulfonyl)azepane 3,4,5-triol (169).
Scheme 29: Synthesis by RCM of tetrahydropyridin-3-ol 171 and tetrahydroazepin-3-ol 173.
