291314-82-4Relevant articles and documents
Continuous-Flow Dynamic Kinetic Resolution of Racemic Alcohols by Lipase–Oxovanadium Cocatalysis
Adebar, Niklas,Akai, Shuji,Gr?ger, Harald,Higashio, Koichi,Kühn, Franziska,Katsuragi, Satoko,Kundu, Dhiman,Plass, Carmen
, p. 1961 - 1967 (2020/04/09)
A continuous-flow dynamic kinetic resolution of racemic secondary alcohols was carried out using a single column reactor packed with a mixture of immobilized lipase and an immobilized oxovanadium species, VMPS4. As a result, optically pure esters were produced in 88–92 % yields. Problems encountered in this study were overcome by using fillers that efficiently maintained the initial distribution of the catalysts in the reactor and by using a packing method in which the mixing ratio of the two catalysts was varied in a stepwise fashion. The flow process led to an increased turnover number of each catalyst compared to those of batch reactions.
One-pot synthesis of optically active allyl esters via lipase-vanadium combo catalysis
Akai, Shuji,Hanada, Ryosuke,Fujiwara, Noboru,Kita, Yasuyuki,Egi, Masahiro
supporting information; experimental part, p. 4900 - 4903 (2011/01/12)
The combination of vanadium-oxo compounds (3 or 4) with a lipase produced the regio- and enantioconvergent transformation of racemic allyl alcohols (1 or 2) into optically active allyl esters. In this system, the vanadium compounds catalyzed the continuous racemization of the alcohols along with the transposition of the hydroxyl group, while the lipase effected the chemo- and enantioselective esterification to achieve the dynamic kinetic resolution.
Enantioselective synthesis of cis-7-methoxy-calamenene via Claisen rearrangement of an enzymatically resolved allyl alcohol
Brenna, Elisabetta,Dei Negri, Claudia,Fuganti, Claudio,Gatti, Francesco G.,Serra, Stefano
, p. 335 - 340 (2007/10/03)
An enantioselective synthesis of cis-7-methoxy-calamenene 1 has been accomplished through the following key-steps: (i) enzymatic resolution of the racemic allyl alcohol 3 to furnish the (R)-enantiomer (ee>99%); (ii) Claisen-orthoester rearrangement of 4 t
Aminocyclopentadienyl Ruthenium Complexes as Racemization Catalysts for Dynamic Kinetic Resolution of Secondary Alcohols at Ambient Temperature
Choi, Jun Ho,Choi, Yoon Kyung,Kim, Yu Hwan,Park, Eun Sil,Kim, Eun Jung,Kim, Mahn-Joo,Park, Jaiwook
, p. 1972 - 1977 (2007/10/03)
Aminocyclopentadienyl ruthenium complexes, which can be used as room-temperature racemization catalysts with lipases in the dynamic kinetic resolution (DKR) of secondary alcohols, were synthesized from cyclopenta-2,4-dienimines, Ru3(CO)12, and CHCl 3: [2,3,4,5-Ph4(η5-C 4CNHR)]Ru-(CO)2Cl (4: R = i-Pr; 5: R = n-Pr; 6: R = t-Bu), [2,5-Me2-3,4-Ph2(η5-C 4CNHR)]Ru(CO)2Cl (7: R = i-Pr; 8: R = Ph), and [2,3,4,5-Ph4(η5-C4CNHAr)]Ru(CO) 2Cl (9: Ar =p-NO2C6H4; 10: Ar = p-ClC6H4; 11: Ar = Ph; 12: Ar = p-OMeC6H 4; 13: Ar = p-NMe2C6H4). The tests in the racemization of (S)-4-phenyl-2-butanol showed that 7 is the most active catalyst, although the difference decreased in the DKR. Complex 4 was used in the DKR of various alcohols; at room temperature, not only simple alcohols but also functionalized ones such as allylic alcohols, alkynyl alcohols, diols, hydroxyl esters, and chlorohydrins were successfully transformed to chiral acetates. In mechanistic studies for the catalytic racemization, ruthenium hydride 14 appeared to be a key species. It was the major organometallic species in the racemization of (S)-1-phenylethanol with 4 and potassium tert-butoxide. In a separate experiment, (S)-1-phenylethanol was racemized catalytically by 14 in the presence of acetophenone.
Dynamic kinetic resolution of allylic alcohols mediated by ruthenium- and lipase-based catalysts.
Lee,Huh,Kim,Jung,Koh,Park
, p. 2377 - 2379 (2007/10/03)
An enzyme-metal combo reaction has been developed for the dynamic kinetic resolution of allylic alcohols in which racemic substrates are transformed by a lipase and a ruthenium complex in the presence of an acyl donor to allylic acetates of high optical purity in over 80% yield.
