112837-29-3Relevant academic research and scientific papers
Asymmetric peroxidation of prochiral allylic and benzylic compounds with tert-butyl hydroperoxide and chiral bisoxazoline-copper complexes
Schulz, Manfred,Kluge, Ralph,Gadissa Gelalcha, Feyissa
, p. 4341 - 4360 (1998)
The first enantioselective peroxidation of prochiral allylic and benzylic C-H compounds by the use of chiral bisoxazoline-copper(I) complexes, generated in situ from the ligands 3 and 4a-d, and t-BuOOH as oxidant is reported. Cyclohexene 1, cyclopentene 5, α-angelica lactone 7, allylbenzene 9 and 2-phenylbutane 11 were converted into the optically active allylic and benzylic tert-butyl peroxides 2, 6, 8, 10a and 12 in good yields and ee values of 4-20%. Oxidations of 1-substituted 1-cyclohexenes 13a-c led to mixtures of regioisomeric peroxides 16a-c, 17a-c and 18a-c with different regio- and enantioselectivities, depending on the 1-substituent and the ligand used. The highest ee values (up to 84%) were observed for (S)-3-tert- butylperoxy-1-methyl-1-cyclohexene 17a.
A concise asymmetric synthesis of the pheromone 1-methylcyclohex-2-enol via a 'merged substitution-elimination reaction'
Hamon, David P. G.,Tuck, Kellie L.
, p. 941 - 942 (1997)
The title compound is prepared (> 94% ee) by a three step synthesis from 1-methylcyclohexene via a 'merged substitution-elimination reaction' involving a phenylselenide ion.
A convenient synthesis of both enantiomers of seudenol and their conversion to 1-methyl-2-cyclohexen-1-ol (MCOL)
Johnston,Morgan,Oehlschlager,Ramaswamy
, p. 377 - 380 (1991)
PPL catalyzed transesterification of seudenol (2) in dry Et2O yielded both optically enriched enantiomers (≥95% ee). Epoxidation, mesylation and reductive ring opening furnished optically enriched MCOL (1).
Privileged phosphine-based metal-organic frameworks for broad-scope asymmetric catalysis
Falkowski, Joseph M.,Sawano, Takahiro,Zhang, Teng,Tsun, Galen,Chen, Yuan,Lockard, Jenny V.,Lin, Wenbin
supporting information, p. 5213 - 5216 (2014/05/06)
A robust and porous Zr metal-organic framework (MOF) based on a BINAP-derived dicarboxylate linker, BINAP-MOF, was synthesized and post-synthetically metalated with Ru and Rh complexes to afford highly enantioselective catalysts for important organic transformations. The Rh-functionalized MOF is not only highly enantioselective (up to >99% ee) but also 3 times as active as the homogeneous control. XAFS studies revealed that the Ru-functionalized MOF contains Ru-BINAP precatalysts with the same coordination environment as the homogeneous Ru complex. The post-synthetically metalated BINAP-MOFs provide a versatile family of single-site solid catalysts for catalyzing a broad scope of asymmetric organic transformations, including addition of aryl and alkyl groups to α,β-unsaturated ketones and hydrogenation of substituted alkene and carbonyl compounds.
Improved synthesis of cyclic tertiary allylic alcohols by asymmetric 1,2-addition of AlMe3 to enones
Kolb, Andreas,Zuo, Wei,Siewert, Juergen,Harms, Klaus,Von Zezschwitz, Paultheo
, p. 16366 - 16373 (2013/12/04)
The development of an improved protocol for the enantioselective Rh I/binap-catalysed 1,2-addition of AlMe3 to cyclic enones is reported. 31P NMR analysis of the reaction revealed that the catalyst in its resting state is a chloride-bridged dimer. This insight led to the use of AgBF4 as an additive for in situ activation of the dimeric precatalyst. Thus, the catalyst loading can now be reduced to only 1 mol % with respect to rhodium. Various 5-7-membered cyclic enones can be transformed into tertiary allylic alcohols with excellent levels of enantioselectivity and high yields. The obtained products are versatile synthetic building blocks, shown by a highly enantioselective formal total synthesis of the pheromone (-)-frontalin as well as formation of a bicyclic lactone that has the core structure of the natural flavour component "wine lactone". Copyright
Simple and efficient 1,3-isomerization of allylic alcohols using a supported monomeric vanadium-oxide catalyst
Mitsudome, Takato,Sueoka, Shoichiro,Ikeda, Satoshi,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
, p. 2879 - 2882 (2013/10/21)
Promotion by group high five: Silica-supported monomeric vanadium-oxide promoted the isomerization of various allylic alcohols, including under scaled-up and solvent-free reaction conditions. This catalyst also exhibited high reusability with no drop in activity.
Simple strategy for synthesis of optically active allylic alcohols and amines by using enantioselective organocatalysis
Jiang, Hao,Holub, Nicole,J?rgensen, Karl Anker
experimental part, p. 20630 - 20635 (2011/10/09)
A simple organocatalytic one-pot protocol for the construction of optically active allylic alcohols and amines using readily available reactants and catalyst is presented. The described reaction is enabled by an enantioselective enone epoxidation/aziridination-Wharton-reaction sequence affording two highly privileged and synthetically important classes of compounds in an easy and benign way. The advantages of the described sequence include easy generation of stereogenic allylic centers, also including quaternary stereocenters, with excellent enantio- and diastereomeric-control and high product diversity. Furthermore, using monosubstituted enones as substrates, having moderate enantiomeric excess, the one-pot reaction sequence proceeds with an enantioenrichment of the products and high diastereoselectivity was achieved.
Asymmetric synthesis of (S)-1-methyl-2-cyclohexen-1-ol, a constituent of the aggregation pheromone of Dendroctonus pseudotsugae
Hamon, David P. G.,Tuck, Kellie L.
, p. 4829 - 4835 (2007/10/03)
1-Methyl-2-cyclohexen-1-ol has been prepared by a three step synthesis from 1-methylcyclohexene, in greater than 94% e.e., via a 'merged substitution-elimination reaction' between NaSePh and 2-methyl-2- hydroxycyclohexyl p-toluenesulphonate. (C) 2000 Elsevier Science Ltd.
Pheromone Synthesis, CXI. - An Enzyme-Mediated Synthesis of Both Enantiomers of Seudenol and 1-Methyl-2-cyclohexen-1-ol, the Aggregation Pheromones of Dendroctonus pseudotsugae
Mori, Kenji,Ogoche, Jondiko I.J.
, p. 903 - 906 (2007/10/02)
Enzymatic resolution of seudenol acetate by pig liver esterase has led to an efficient preparation of both the enantiomers of seudenol and 1-methyl-2-cyclohexen-1-ol, the aggregation pheromones of the Douglas-fir beetle Dendroctonus pseudotsugae Hopkins.
