216160-44-0Relevant academic research and scientific papers
Organomagnesium Based Flash Chemistry: Continuous Flow Generation and Utilization of Halomethylmagnesium Intermediates
Von Keutz, Timo,Cantillo, David,Kappe, C. Oliver
supporting information, p. 7537 - 7541 (2020/10/12)
The generation of highly unstable chloromethylmagnesium chloride in a continuous flow reactor and its reaction with aldehydes and ketones is reported. With this strategy, chlorohydrins and epoxides were synthesized within a total residence time of only 2.6 s. The outcome of the reaction can be tuned by simply using either a basic or an acidic quench. Very good to excellent isolated yields, up to 97%, have been obtained for most cases (30 examples).
External trapping of halomethyllithium enabled by flow microreactors
Degennaro, Leonardo,Fanelli, Flavio,Giovine, Arianna,Luisi, Renzo
supporting information, p. 21 - 27 (2015/01/30)
This work demonstrates that the accurate control of the reaction parameters realized within microreactor systems allowed for a taming of the reactivity of thermally unstable intermediates such as haloalkyllithiums. The first example of effective external trapping of a reactive carbenoid such as the chloromethyllithium is described. By using microreactor systems, a continuous flow synthesis of chloro alcohols and chloro amines could be achieved with high yields. By controlling the residence time the highly reactive chloromethyllithium could be generated and reacted with electrophiles at temperatures much higher than in batch-mode and without internal quenching. The developed continuous-flow process matches the requirements for sustainability.
Highly enantioselective acylation of chlorohydrins using Amano AK lipase from P. fluorescens immobilized on silk fibroin-alginate spheres
Ferreira, Irlon M.,Nishimura, Rodolfo H.V.,Souza, Ana B. Dos A.,Clososki, Giuliano C.,Yoshioka, Sergio A.,Porto, André L.M.
supporting information, p. 5062 - 5065 (2015/01/09)
Aromatic, allylic, and aliphatic compounds containing a chlorohydrin group were selected as substrates for the enzymatic kinetic resolution mediated by Amano AK lipase from Pseudomonas fluorescens immobilized in silk friboin-alginate spheres. Thus, the en
Efficient synthesis of chlorohydrins using ClCH2MgCl·LiCl
Nishimura, Rodolfo H.V.,Toledo, Fabiano T.,Lopes, Jo?o L.C.,Clososki, Giuliano C.
, p. 287 - 290 (2013/02/23)
The mixed lithium-magnesium carbenoid ClCH2MgCl·LiCl was easily generated in THF through the reaction of chloroiodomethane with i-PrMgCl·LiCl at -78 °C. This reagent reacts well with a number of aldehydes to give the corresponding chlorohydrins in good yields.
Dynamic kinetic resolution of racemic β-haloalcohols: Direct access to enantioenriched epoxides
Haak, Robert M.,Berthiol, Florian,Jerphagnon, Thomas,Gayet, Arnaud J. A.,Tarabiono, Chiara,Postema, Christiaan P.,Ritleng, Vincent,Pfeffer, Michel,Janssen, Dick B.,Minnaard, Adriaan J.,Feringa, Ben L.,De Vries, Johannes G.
supporting information; body text, p. 13508 - 13509 (2009/02/06)
The direct chemo-enzymatic DKR of racemic β-haloalcohols is reported, yielding the corresponding optically active epoxides in a single step. The mutant haloalcohol dehalogenase HheC Cys153Ser Trp249Phe is used for the asymmetric ring closure, whereas racemization of the remaining enantiomer of the haloalcohol is achieved using the new iridacycle 3, one of the most effective racemization catalysts to date for β-haloalcohols. Copyright
'Green' synthesis of important pharmaceutical building blocks: Enzymatic access to enantiomerically pure α-chloroalcohols
Zhu, Dunming,Mukherjee, Chandrani,Hua, Ling
, p. 3275 - 3278 (2007/10/03)
Thirty one recombinant ketoreductase enzymes were screened for the reduction of six α-chloroketones, the precursors of pharmaceutically valuable α-chloroalcohols. Several highly active and enantioselective ketoreductases were found and their applications
Electronic effect on the regioselectivity in the ring opening of para-substituted phenyloxiranes by acetylides
Shindo, Mitsuru,Sugioka, Tomoyuki,Shishido, Kozo
, p. 9265 - 9268 (2007/10/03)
The electronic effect on the regioselectivity in the alkynylation of phenyloxiranes was investigated using three kinds of metal acetylides. BF 3 mediated lithium acetylide provided either the α- or β-alkynylated products by controlling the effe
Highly enantioselective and regioselective biocatalytic azidolysis of aromatic epoxides
Spelberg, Jeffrey H. Lutje,Van Vlieg, Johan E. T. Hylckama,Tang, Lixia,Janssen, Dick B.,Kellogg, Richard M.
, p. 41 - 43 (2007/10/03)
(equation presented) The halohydrin dehalogenase from Agrobacterium radiobacter AD1 catalyzed the highly enantioselective and β-regioselective azidolysis of (substituted) styrene oxides. By means of kinetic resolutions the remaining epoxide and the formed azido alcohol could be obtained in very high ee. In a large scale conversion, the decrease in yield and selectivity due to the uncatalyzed chemical side reaction could be overcome by slow addition of azide.
anti-Prelog microbial reduction of aryl α-halomethyl or α- hydroxymethyl ketones with Geotrichum sp. 38
Wei, Zhi-Liang,Li, Zu-Yi,Lin, Guo-Qiang
, p. 13059 - 13072 (2007/10/03)
Reduction of aryl α-halomethyl ketones 5a-d and 7a-h and α- hydroxymethyl ketones 10a-b by Geotrichum sp. 38 affording mostly the anti- Prelog alcohols was reported and the stereoselectivities of the reductive products were discussed.
