Synthesis and properties of tetrathiafulvalenes bearing 6-aryl-1,4-dithiafulvenes
- Aya Yoshimura,
- Hitoshi Kimura,
- Kohei Kagawa,
- Mayuka Yoshioka,
- Toshiki Itou,
- Dhananjayan Vasu,
- Takashi Shirahata,
- Hideki Yorimitsu and
- Yohji Misaki
Beilstein J. Org. Chem. 2020, 16, 974–981, doi:10.3762/bjoc.16.86
Graphical Abstract
Figure 1: Target compounds.
Scheme 1: Synthesis of compounds 3.
Scheme 2: Synthesis of compound 4.
Figure 2: An optimized structure of 1a. a) Top view, b) side view, and c) labeling of the 1,3-dithiole rings.
Figure 3: Molecular orbitals of 1a.
Figure 4: Cyclic voltammograms of 1a,b, 2a, and 4 in PhCN/CS2 1:1 (v/v) solution.
Figure 5: Related compound 14.
Homolytic substitution at phosphorus for C–P bond formation in organic synthesis
- Hideki Yorimitsu
Beilstein J. Org. Chem. 2013, 9, 1269–1277, doi:10.3762/bjoc.9.143
Graphical Abstract
Scheme 1: Representative C–P bond-forming reactions.
Scheme 2: General equation of homolytic substitution.
Scheme 3: Addition of diphenyl(triphenylstannyl)phosphine.
Scheme 4: Addition of diphenyl(trimethylstannyl)phosphine.
Scheme 5: Plausible mechanism of addition of R3Sn–PPh2.
Scheme 6: Addition of tetraorganodiphosphines to phenylacetylene.
Scheme 7: Plausible mechanism of anti-diphosphination.
Scheme 8: Radical diphosphination for synthesizing fluorescent material.
Scheme 9: Mechanism of thiophosphination with diphenyl(organosulfanyl)phosphine.
Scheme 10: Thiophosphination with S-thiophosphinyl O-ethyl dithiocarbonate.
Scheme 11: Photoinduced selenophosphination of allenes.
Scheme 12: Photoinduced tellurophosphination.
Scheme 13: Decarboxylative phosphorylation of carboxylic acid derivatives.
Scheme 14: Plausible mechanism of decarboxylative phosphorylation.
Scheme 15: Radical phosphination of PTOC esters with white phosphorus.
Scheme 16: Plausible mechanism of radical phosphination (Si = (Me3Si)3Si).
Scheme 17: Stereoselective phosphination leading to (S,S)-aminophosphine derivative.
Figure 1: Calculated reaction profile of homolytic substitution between Ph• and Me3Sn–PPh2 at the B2-PLYP-D/T...
Scheme 18: Phosphination with retention of axial chirality.
Scheme 19: Chemodivergent phosphination.
Scheme 20: Bis(phosphoryl)-bridged biphenyls by radical phosphination.
Scheme 21: Bis(phosphoryl)-bridged ladder triphenylene by radical phosphination.
Scheme 22: Photoinduced phosphination of perfluoroalkyl iodides with tetraphenyldiphosphine.
Scheme 23: Ti(III)-mediated radical phosphination of organic bromides with white phosphorus.
Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation
- Kei Murakami and
- Hideki Yorimitsu
Beilstein J. Org. Chem. 2013, 9, 278–302, doi:10.3762/bjoc.9.34
Graphical Abstract
Scheme 1: Variation of substrates for carbomagnesiation and carbozincation in this article.
Scheme 2: Copper-catalyzed arylmagnesiation and allylmagnesiation of alkynyl sulfone.
Scheme 3: Copper-catalyzed four-component reaction of alkynyl sulfoxide with alkylzinc reagent, diiodomethane...
Scheme 4: Rhodium-catalyzed reaction of aryl alkynyl ketones with arylzinc reagents.
Scheme 5: Allylmagnesiation of propargyl alcohol, which provides the anti-addition product.
Scheme 6: Negishi’s total synthesis of (Z)-γ-bisabolene by allylmagnesiation.
Scheme 7: Iron-catalyzed syn-carbomagnesiation of propargylic or homopropargylic alcohol.
Scheme 8: Mechanism of iron-catalyzed carbomagnesiation.
Scheme 9: Regio- and stereoselective manganese-catalyzed allylmagnesiation.
Scheme 10: Vinylation and alkylation of arylacetylene-bearing hydroxy group.
Scheme 11: Arylmagnesiation of (2-pyridyl)silyl-substituted alkynes.
Scheme 12: Synthesis of tamoxifen from 2g.
Scheme 13: Controlling regioselectivity of carbocupration by attaching directing groups.
Scheme 14: Rhodium-catalyzed carbozincation of ynamides.
Scheme 15: Synthesis of 4-pentenenitriles through carbometalation followed by aza-Claisen rearrangement.
Scheme 16: Uncatalyzed carbomagnesiation of cyclopropenes.
Scheme 17: Iron-catalyzed carbometalation of cyclopropenes.
Scheme 18: Enantioselective carbozincation of cyclopropenes.
Scheme 19: Copper-catalyzed facially selective carbomagnesiation.
Scheme 20: Arylmagnesiation of cyclopropenes.
Scheme 21: Enantioselective methylmagnesiation of cyclopropenes without catalyst.
Scheme 22: Copper-catalyzed carbozincation.
Scheme 23: Enantioselective ethylzincation of cyclopropenes.
Scheme 24: Nickel-catalyzed ring-opening aryl- and alkenylmagnesiation of a methylenecyclopropane.
Scheme 25: Reaction mechanism.
Scheme 26: Nickel-catalyzed carbomagnesiation of arylacetylene and dialkylacetylene.
Scheme 27: Nickel-catalyzed carbozincation of arylacetylenes and its application to the synthesis of tamoxifen....
Scheme 28: Bristol-Myers Squibb’s nickel-catalyzed phenylzincation.
Scheme 29: Iron/NHC-catalyzed arylmagnesiation of aryl(alkyl)acetylene.
Scheme 30: Iron/copper-cocatalyzed alkylmagnesiation of aryl(alkyl)acetylenes.
Scheme 31: Iron-catalyzed hydrometalation.
Scheme 32: Iron/copper-cocatalyzed arylmagnesiation of dialkylacetylenes.
Scheme 33: Chromium-catalyzed arylmagnesiation of alkynes.
Scheme 34: Cobalt-catalyzed arylzincation of alkynes.
Scheme 35: Cobalt-catalyzed formation of arylzinc reagents and subsequent arylzincation of alkynes.
Scheme 36: Cobalt-catalyzed benzylzincation of dialkylacetylene and aryl(alkyl)acetylenes.
Scheme 37: Synthesis of estrogen receptor antagonist.
Scheme 38: Cobalt-catalyzed allylzincation of aryl-substituted alkynes.
Scheme 39: Silver-catalyzed alkylmagnesiation of terminal alkyne.
Scheme 40: Proposed mechanism of silver-catalyzed alkylmagnesiation.
Scheme 41: Zirconium-catalyzed ethylzincation of terminal alkenes.
Scheme 42: Zirconium-catalyzed alkylmagnesiation.
Scheme 43: Titanium-catalyzed carbomagnesiation.
Scheme 44: Three-component coupling reaction.
Scheme 45: Iron-catalyzed arylzincation reaction of oxabicyclic alkenes.
Scheme 46: Reaction of allenyl ketones with organomagnesium reagent.
Scheme 47: Regio- and stereoselective reaction of a 2,3-allenoate.
Scheme 48: Three-component coupling reaction of 1,2-allenoate, organozinc reagent, and ketone.
Scheme 49: Proposed mechanism for a rhodium-catalyzed arylzincation of allenes.
Scheme 50: Synthesis of skipped polyenes by iterative arylzincation/allenylation reaction.
Scheme 51: Synthesis of 1,4-diorganomagnesium compound from 1,2-dienes.
Scheme 52: Synthesis of tricyclic compounds.
Scheme 53: Manganese-catalyzed allylmagnesiation of allenes.
Scheme 54: Copper-catalyzed alkylmagnesiation of 1,3-dienes and 1,3-enynes.
Scheme 55: Chromium-catalyzed methallylmagnesiation of 1,6-diynes.
Scheme 56: Chromium-catalyzed allylmagnesiation of 1,6-enynes.
Scheme 57: Proposed mechanism of the chromium-catalyzed methallylmagnesiation.
