Rhodium-Catalyzed Chemo- and Regioselective Intermolecular Cross-Cyclotrimerization of Nonactivated Terminal and Internal Alkynes.

@article{Nishigaki2017RhodiumCatalyzedCA,
  title={Rhodium-Catalyzed Chemo- and Regioselective Intermolecular Cross-Cyclotrimerization of Nonactivated Terminal and Internal Alkynes.},
  author={Shuhei Nishigaki and Yu Shibata and Ken Tanaka},
  journal={The Journal of organic chemistry},
  year={2017},
  volume={82 20},
  pages={
          11117-11125
        }
}
It has been established that a cationic rhodium(I)/BIPHEP complex is able to catalyze the unprecedented intermolecular cross-cyclotrimerization of nonactivated terminal and internal alkynes at room temperature. In this transformation, the use of arylacetylenes as terminal alkynes and 1,4-butynediol derivatives as internal alkynes afforded the cross-cyclotrimerization products with good chemo- and regioselectivity. The present study clearly demonstrated that an electronically biased combination… Expand
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References

SHOWING 1-10 OF 54 REFERENCES
Highly chemo- and regioselective intermolecular cyclotrimerization of alkynes catalyzed by cationic rhodium(I)/modified BINAP complexes.
TLDR
A noteworthy example of intermolecular cocyclotrimerization of two different alkynes in terms of catalytic activity, chemo- and regioselectivity, scope of substrates, and ease of operation is demonstrated. Expand
Highly chemo-, regio-, and enantioselective rhodium-catalyzed cross-cyclotrimerization of two different alkynes with alkenes.
It has been established that a cationic rhodium(I)/(R)-tol-binap complex catalyzes the cross-cyclotrimerization of silylacetylenes, di-tert-butyl acetylenedicarboxylates, and acrylamides withExpand
Totally chemo- and regioselective cobalt(I)-mediated formal intermolecular cyclotrimerization of alkynes.
TLDR
The first examples of totally chemo- and regioselective formal intermolecular cobalt(I)-catalyzed [2 + 2 + 2] cyclizations of three different alkynes are reported. Expand
Ru(II)-catalyzed chemo- and regioselective cyclotrimerization of three unsymmetrical alkynes through boron temporary tether. One-pot four-component coupling via cyclotrimerization/Suzuki-Miyaura coupling.
The Ru(II)-catalyzed [2+2+2] cyclotrimerization of alkynylboronates, propargyl alcohol, and terminal alkynes proceeded chemo- and regioselectively to give rise to arylboronates, which were subjectedExpand
Cp(*)RuCl-catalyzed formal intermolecular cyclotrimerization of three unsymmetrical alkynes through a boron temporary tether: regioselective four-component coupling synthesis of phthalides.
TLDR
The perfect regioselectivity of the ruthenium-catalyzed formal intermolecular cyclotrimerization was discussed on the basis of the density functional calculations of a boraruthenacycle intermediate. Expand
Chemo- and regioselective intermolecular cyclotrimerization of terminal alkynes catalyzed by cationic rhodium(I)/modified BINAP complexes: application to one-step synthesis of paracyclophanes.
TLDR
A highly regioselective intermolecular cyclotrimerization of terminal alkynes has been developed based on the use of the cationic rhodium(I)/DTBM-Segphos complex, furnishing 3,6-disubstituted phthalates in high yields. Expand
Synthesis of [8]Cycloparaphenylene-octacarboxylates via Rh-Catalyzed Stepwise Cross-Alkyne Cyclotrimerization.
TLDR
Both absorption and fluorescence maxima of [8]CPP-octacarboxylates in CHCl3 were significantly blue-shifted compared to those of C4- and C2-symmetrical due to the presence of eight electron-withdrawing ester moieties. Expand
Ruthenium-catalyzed [2+2+2] cycloaddition of three different alkynes
Abstract A chemoselective [2 + 2 + 2] cycloaddition of an internal alkyne, a terminal alkyne and dimethyl acetylenedicarboxylate was efficiently catalyzed by Cp * RuCl(cod) to give trisubstituted oExpand
[Ir(cod)Cl]2/FDPPE-Catalyzed Chemo- and Regioselective Cyclotrimerization of Two Different Terminal Alkynes To Give 1,3,5-Trisubstituted Benzenes
[Ir(cod)Cl] 2 in combination with 1,2-bis(dipentafluorophenylphosphino)ethane catalyzes chemo- and regioselective cyclotrimerization of two different alkynes. The reaction of methyl propiolate withExpand
Ruthenium-catalysed synthesis of o-phthalates by highly chemoselective intermolecular [2+2+2] cycloaddition of terminal alkynes and dimethyl acetylenedicarboxylate
Abstract A highly chemoselective intermolecular [2+2+2] cycloaddition of 2 eq. of terminal alkynes with dimethyl acetylenedicarboxylate, which enables the straightforward synthesis of dialkylated oExpand
...
1
2
3
4
5
...