Sigmatropic rearrangements of cyclopropenylcarbinol derivatives. Access to diversely substituted alkylidenecyclopropanes
- Guillaume Ernouf,
- Jean-Louis Brayer,
- Christophe Meyer and
- Janine Cossy
Beilstein J. Org. Chem. 2019, 15, 333–350, doi:10.3762/bjoc.15.29
Graphical Abstract
Scheme 1: Representative strategies for the formation of alkylidenecyclopropanes from cyclopropenes and scope...
Scheme 2: [2,3]-Sigmatropic rearrangement of phosphinites 2a–h.
Scheme 3: [2,3]-Sigmatropic rearrangement of a phosphinite derived from enantioenriched cyclopropenylcarbinol...
Scheme 4: Selective reduction of phosphine oxide (E)-3f.
Scheme 5: Attempted thermal [2,3]-sigmatropic rearrangement of phosphinite 6a.
Scheme 6: Computed activation barriers and free enthalpies.
Scheme 7: [2,3]-Sigmatropic rearrangement of phosphinites 6a–j.
Scheme 8: Proposed mechanism for the Lewis base-catalyzed rearrangement of phosphinites 6.
Scheme 9: [3,3]-Sigmatropic rearrangement of tertiary cyclopropenylcarbinyl acetates 10a–c.
Scheme 10: [3,3]-Sigmatropic rearrangement of secondary cyclopropenylcarbinyl esters 10d–h.
Scheme 11: [3,3]-Sigmatropic rearrangement of trichoroacetimidates 12a–i.
Scheme 12: Reaction of trichloroacetamide 13f with pyrrolidine.
Scheme 13: Catalytic hydrogenation of (arylmethylene)cyclopropropane 13f.
Scheme 14: Instability of trichloroacetimidates 21a–c derived from cyclopropenylcarbinols 20a–c.
Scheme 15: [3,3]-Sigmatropic rearrangement of cyanate 27 generated from cyclopropenylcarbinyl carbamate 26.
Scheme 16: Synthesis of alkylidene(aminocyclopropane) derivatives 30–37 from carbamate 26.
Scheme 17: Scope of the dehydration–[3,3]-sigmatropic rearrangement sequence of cyclopropenylcarbinyl carbamat...
Scheme 18: Formation of trifluoroacetamide 50 from carbamate 49.
Scheme 19: Formation of alkylidene[(N-trifluoroacetylamino)cyclopropanes] 51–54.
Scheme 20: Diastereoselective hydrogenation of alkylidenecyclopropane 51.
Scheme 21: Ireland–Claisen rearrangement of cyclopropenylcarbinyl glycolates 56a–l.
Scheme 22: Synthesis and Ireland–Claisen rearrangement of glycolate 61 possessing gem-diester substitution at ...
Scheme 23: Synthesis of alkylidene(gem-difluorocyclopropanes) 66a–h, and 66k–n from propargyl glycolates 64a–n....
Scheme 24: Ireland–Claisen rearrangement of N,N-diBoc glycinates 67a and 67b.
Scheme 25: Diastereoselective hydrogenation of alkylidenecyclopropanes 58a and 74.
Scheme 26: Synthesis of functionalized gem-difluorocyclopropanes 76 and 77 from alkylidenecyclopropane 66a.
Scheme 27: Access to oxa- and azabicyclic compounds 78–80.
Beyond catalyst deactivation: cross-metathesis involving olefins containing N-heteroaromatics
- Kevin Lafaye,
- Cyril Bosset,
- Lionel Nicolas,
- Amandine Guérinot and
- Janine Cossy
Beilstein J. Org. Chem. 2015, 11, 2223–2241, doi:10.3762/bjoc.11.241
Graphical Abstract
Figure 1: Some ruthenium catalysts for metathesis reactions.
Scheme 1: Decomposition of methylidenes 1 and 2.
Scheme 2: Deactivation of G-HII in the presence of ethylene.
Scheme 3: Reaction between GI/GII and n-BuNH2.
Scheme 4: Reaction of GII with amines a–d.
Scheme 5: Amine-induced decomposition of GII methylidene 2.
Scheme 6: Amine-induced decomposition of GII in RCM conditions.
Scheme 7: Deactivation of methylidene 2 in the presence of pyridine.
Scheme 8: Reaction of G-HII with various amines.
Scheme 9: Formation of olefin 22 from styrene.
Scheme 10: Hypothetic deactivation pathway of G-HII.
Scheme 11: RCM of dienic pyridinium salts.
Scheme 12: Synthesis of polycyclic scaffolds using RCM.
Scheme 13: Enyne ring-closing metathesis.
Scheme 14: Synthesis of (R)-(+)-muscopyridine using a RCM strategy.
Scheme 15: Synthesis of a tris-pyrrole macrocycle.
Scheme 16: Synthesis of a bicyclic imidazole.
Scheme 17: RCM using Schrock’s catalyst 44.
Scheme 18: Synthesis of 1,6-pyrido-diazocine 46 by using a RCM.
Scheme 19: Synthesis of fused pyrimido-azepines through RCM.
Scheme 20: RCM involving alkenes containing various N-heteroaromatics.
Scheme 21: Synthesis of dihydroisoquinoline using a RCM.
Scheme 22: Formation of tricyclic compound 59.
Scheme 23: RCM in the synthesis of normuscopyridine.
Scheme 24: Synthesis of macrocycle 64.
Scheme 25: Synthesis of macrocycles possessing an imidazole group.
Scheme 26: Retrosynthesis of an analogue of erythromycin.
Scheme 27: Retrosynthesis of haminol A.
Scheme 28: CM involving 3-vinylpyridine 70 with 71 and vinylpyridine 70 with 73.
Scheme 29: Revised retrosynthesis of haminol A.
Scheme 30: CM between 78 and crotonaldehyde.
Scheme 31: Hypothesized deactivation pathway.
Scheme 32: CM involving an allyl sulfide containing a quinoline.
Scheme 33: CM involving allylic sulfide possessing a quinoxaline or a phenanthroline.
Scheme 34: CM between an acrylate and a 2-methoxy-5-bromo pyridine.
Scheme 35: Successful CM of an alkene containing a 2-chloropyridine.
Scheme 36: Variation of the substituent on the pyridine ring.
Scheme 37: CM involving alkenes containing a variety of N-heteroaromatics.
When cyclopropenes meet gold catalysts
- Frédéric Miege,
- Christophe Meyer and
- Janine Cossy
Beilstein J. Org. Chem. 2011, 7, 717–734, doi:10.3762/bjoc.7.82
Graphical Abstract
Scheme 1: General reactivity of cyclopropenes in the presence of gold catalysts.
Scheme 2: Cationic organogold species generated from cyclopropenone acetals.
Scheme 3: Rotation barriers around the C2–C3 bond (M06 DFT calculations).
Scheme 4: Au–C1 bond length in organogold species of type D.
Scheme 5: Gold-catalyzed addition of alcohols or water to cyclopropene 8.
Scheme 6: Gold-catalyzed addition of alcohols to cyclopropene 10.
Scheme 7: Mechanism of the gold-catalyzed addition of alcohols to cyclopropenes.
Scheme 8: Synthesis of tert-allylic ethers from cyclopropenes and allenes.
Scheme 9: Oxidation of the intermediate gold–carbene with diphenylsulfoxide.
Scheme 10: Gold, copper and Lewis acid-catalyzed reactions of cyclopropene 18.
Scheme 11: Mechanism of the Lewis acid-catalyzed reactions of cyclopropene 18.
Scheme 12: Gold-catalyzed rearrangement of vinylcyclopropenes 25.
Scheme 13: Gold-catalyzed rearrangement of cyclopropenes 27 to indenes 28.
Scheme 14: Gold-catalyzed rearrangement of cyclopropenes 29 to indenes 30.
Scheme 15: Gold-catalyzed rearrangement of cyclopropenyl ester 34a.
Scheme 16: Gold-catalyzed reactions of cyclopropenyl esters 34b–34d.
Scheme 17: Gold-catalyzed reactions of cyclopropenylsilane 34e.
Scheme 18: Gold-catalyzed rearrangement of cyclopropenylmethyl acetates.
Scheme 19: Mechanism of the gold-catalyzed rearrangement of cyclopropenes 39.
Scheme 20: Gold-catalyzed cyclopropanation of styrene with cyclopropene 8.
Scheme 21: Representative reactions of carbene precursors on gold metal.
Scheme 22: Intermolecular olefin cyclopropanation with gold carbenes generated from cyclopropenes.
Scheme 23: Gold-catalyzed formation of trienes from cyclopropenes and furans.
Scheme 24: Gold-catalyzed formation of trienes from cyclopropenes and furans.
Scheme 25: Gold-catalyzed formation of trienes from cyclopropenes and furans.
Scheme 26: Gold-catalyzed cycloisomerization of cyclopropene-ene 59.
Scheme 27: Gold-catalyzed cycloisomerization of substituted allyl cyclopropenyl carbinyl ethers 62a–62f.
Scheme 28: Gold-catalyzed cycloisomerization of cyclopropene-enes.
Scheme 29: Gold-catalyzed cycloisomerization of cyclopropene-ynes.
Scheme 30: Formation of products arising from a double cleavage process in the gold-catalyzed cycloisomerizati...
Scheme 31: Gold-catalyzed cycloisomerization of cyclopropene-ynes involving a double cleavage process.
Scheme 32: Gold-catalyzed reaction of cyclopropene-ynes, cyclopropene-enes and cyclopropene-allenes.
