129047-18-3Relevant academic research and scientific papers
Controlling the regiochemistry of nucleophilic attack on unsymmetrical allyl complexes
Faller, J.W.,Lambert, C.,Mazzieri, M.R.
, p. 161 - 177 (1990)
The NO and CO ligands in a 3-allyl)>+ complex exert differential electronic effects on the allyl moiety and control the regiochemistry of nucleophilic attack.These directing influences are sufficiently strong that they overcome the normal directing influences of substituents of the allyl moiety.An essential task, therefore, is arranging for the appropriate terminus of the allyl to have the relationship to the nitrosyl group that will result in attack at the desired location.Replacement of a single CO ligand in a neutral monosubstituted allyl complex of CpMo(CO)2 with NO+ yields a product for which addition occurs at the unsubstituted end of the allyl.Hence, an E-olefin with no newly created chiral centres is formed upon nucleophilic attack.A new synthetic strategy has been developed which allows us to build a chiral center in the allylic position of a terminal olefin.Sequential addition of two nucleophiles to a CpMo(NO)(CO)(allyl)+ cation creates these chiral centers, which were not accessible by addition of NO+ to the dicarbonyl.Addition of nucleophiles to homochiral (Neomenthylcyclopentadienyl)Mo(NO)(CO)(phenylallyl)+ complexes yields chiral olefins in high enantiomeric purity.The cationic phenylallyl complexes prepared by different routes were identified by single crystal X-ray diffraction determinations. endo-cis-syn-3-CH(Ph)CHCH2)>BF4 crystallizes in the monoclinic space group P21/n with a 8.226(2), b 12.273(2), c 16.051(2) Angstroem, β 100.02(2)deg, V 1595.7(9) Angstroem3, Z = 4. exo-cis-syn-3-CH(Ph)CHCH2)>BF4 crystallizes in the monoclinic space group P21/c with a 10.706(3), b 14.700(4), c 10.491(3) Angstroem, β 96.48(2)deg, V 1640.5 Angstroem3, Z = 4.
Rhodium-catalyzed olefin isomerization/allyl claisen rearrangement/ intramolecular hydroacylation cascade
Okamoto, Ryuichi,Tanaka, Ken
supporting information, p. 2112 - 2115 (2013/06/05)
It has been established that a cationic Rh(I)/dppf complex catalyzes the olefin isomerization/allyl Claisen rearrangement/intramolecular hydroacylation cascade of di(allyl) ethers to produce substituted cyclopentanones in good yields under mild conditions.
Chemo- and regioselectivity-tunable Pd-catalyzed allylic alkylation of imines
Chen, Jian-Ping,Peng, Qian,Lei, Bai-Lin,Hou, Xue-Long,Wu, Yun-Dong
supporting information; experimental part, p. 14180 - 14183 (2011/10/13)
α-Carbanions of cyclic and acyclic imines have been successfully applied as nucleophiles in the Pd-catalyzed allylic alkylation reaction. Tuning of chemo- and regioselectivity has been realized by using t-BuOK/THF and LDA/toluene to give branched and line
