Cobalt- and rhodium-catalyzed carboxylation using carbon dioxide as the C1 source
- Tetsuaki Fujihara and
- Yasushi Tsuji
Beilstein J. Org. Chem. 2018, 14, 2435–2460, doi:10.3762/bjoc.14.221
Graphical Abstract
Scheme 1: Optimization of the Co-catalyzed carboxylation of 1a.
Scheme 2: Co-catalyzed carboxylation of propargyl acetates 1.
Scheme 3: Plausible reaction mechanism for the Co-catalyzed carboxylation of propargyl acetates 1.
Scheme 4: Optimization of the Co-catalyzed carboxylation of 3a.
Scheme 5: Co-catalyzed carboxylation of vinyl triflates 3.
Scheme 6: Co-catalyzed carboxylation of a sterically hindered aryl triflate 5.
Scheme 7: Optimization of the Co-catalyzed carboxylation of 7a.
Scheme 8: Scope of the reductive carboxylation of α,β-unsaturated nitriles 7.
Scheme 9: Scope of the carboxylation of α,β-unsaturated carboxamides 9.
Scheme 10: Optimization of the Co-catalyzed carboxylation of 11a.
Scheme 11: Scope of the carboxylation of allylarenes 11.
Scheme 12: Scope of the carboxylation of 1,4-diene derivatives 14.
Scheme 13: Plausible reaction mechanism for the Co-catalyzed C(sp3)–H carboxylation of allylarenes.
Scheme 14: Optimization of the Co-catalyzed carboxyzincation of 16a.
Scheme 15: Derivatization of the carboxyzincated product.
Scheme 16: Co-catalyzed carboxyzincation of alkynes 16.
Scheme 17: Plausible reaction mechanism for the Co-catalyzed carboxyzincation of alkynes 16.
Scheme 18: Co-catalyzed four-component coupling of alkynes 16, acrylates 18, CO2, and zinc.
Scheme 19: Proposed reaction mechanism for the Co-catalyzed four-component coupling.
Scheme 20: Visible-light-driven hydrocarboxylation of alkynes.
Scheme 21: Visible-light-driven synthesis of γ-hydroxybutenolides from ortho-ester-substituted aryl alkynes.
Scheme 22: One-pot synthesis of coumarines and 2-quinolones via hydrocarboxylation/alkyne isomerization/cycliz...
Scheme 23: Proposed reaction mechanism for the Co-catalyzed carboxylative cyclization of ortho-substituted aro...
Scheme 24: Rh-catalyzed carboxylation of arylboronic esters 25.
Scheme 25: Rh-catalyzed carboxylation of alkenylboronic esters 27.
Scheme 26: Plausible reaction mechanism for the Rh-catalyzed carboxylation of arylboronic esters 25.
Scheme 27: Ligand effect on the Rh-catalyzed carboxylation of 2-phenylpyridine 29a.
Scheme 28: Rh-catalyzed chelation-assisted C(sp2)–H bond carboxylation with CO2.
Scheme 29: Reaction mechanism for the Rh-catalyzed C(sp2)–H carboxylation of 2-pyridylarenes 29.
Scheme 30: Carboxylation of C(sp2)–H bond with CO2.
Scheme 31: Carboxylation of C(sp2)–H bond with CO2.
Scheme 32: Reaction mechanism for the Rh-catalyzed C(sp2)–H carboxylation of 2-arylphenols 34.
Scheme 33: Hydrocarboxylation of styrene derivatives with CO2.
Scheme 34: Hydrocarboxylation of α,β-unsaturated esters with CO2.
Scheme 35: Asymmetric hydrocarboxylation of α,β-unsaturated esters with CO2.
Scheme 36: Proposed reaction mechanism for the Rh-catalyzed hydrocarboxylation of C–C double bonds with CO2.
Scheme 37: Visible-light-driven hydrocarboxylation with CO2.
Scheme 38: Visible-light-driven Rh-catalyzed hydrocarboxylation of C–C double bonds with CO2.
Scheme 39: Optimization of reaction conditions on the Rh-catalyzed [2 + 2 + 2] cycloaddition of diyne 42a and ...
Scheme 40: [2 + 2 + 2] Cycloaddition of diyne and CO2.
Scheme 41: Proposed reaction pathways for the Rh-catalyzed [2 + 2 + 2] cycloaddition of diyne and CO2.
Synthesis of an organic-soluble π-conjugated [3]rotaxane via rotation of glucopyranose units in permethylated β-cyclodextrin
- Jun Terao,
- Yohei Konoshima,
- Akitoshi Matono,
- Hiroshi Masai,
- Tetsuaki Fujihara and
- Yasushi Tsuji
Beilstein J. Org. Chem. 2014, 10, 2800–2808, doi:10.3762/bjoc.10.297
Graphical Abstract
Figure 1: Synthesis of [1]rotaxane by self-inclusion of a host–guest-linked molecule: a) short molecular leng...
Figure 2: Synthesis of an insulated molecule via flipping phenomenon.
Scheme 1: The synthetic route to the PMβ-CD based linked [3]rotaxane with a 5,15-di([1,1'-biphenyl]-4-yl)porp...
Figure 3: The aromatic region of the 1H NMR spectra of 5 at 25 °C: 1) CDCl3, 2) CD3OD, and 3) CD3OD:D2O 1:1.
Scheme 2: Selective synthesis of fixed [3]rotaxane by Suzuki cross-coupling reaction.
Scheme 3: The synthetic routes to precursor of PM β-CD based insulated oligothiophene.
Scheme 4: Synthesis of dibromohexa(para-phenylene) with two PMCDs 20.
Scheme 5: Synthesis of pseudo-linked [3]rotaxanes via double self-inclusion through flipping.
Figure 4: The aromatic region of the 1H NMR spectra of 5 at 25 °C: 1) CDCl3, 2) CD3OD, and CD3OD/D2O 1:1.
Figure 5: The aromatic region of the 1H NMR spectra of 20 at 25 °C: 1) CDCl3, 2) CD3OD, and CD3OD/D2O 1:1.
Scheme 6: Synthesis of fixed [3]rotaxane via complexation with rhodium porphyrin.
Figure 6: Partial ROESY NMR spectrum of 26 (400 MHz, CDCl3) showing the NOEs between aromatic protons of the ...
