108530-08-1Relevant articles and documents
Enantioselective synthesis of the farnesyltransferase inhibitor, A-345665.0
Rozema, Michael J.,Fickes, Michael,McLaughlin, Maureen,Rohde, Bridget,McDermott, Todd
, p. 8765 - 8768 (2006)
The stereoselective synthesis of A-345665.0 1, a novel farnesyl transferase inhibitor, is described. The key step involves a stereoselective addition of an imidazolyl Grignard reagent to aldehyde 8 in the presence of an external chiral auxiliary. Crystall
SuFEx-enabled, chemoselective synthesis of triflates, triflamides and triflimidates
Alonso, Mercedes,De Borggraeve, Wim M.,Demaerel, Joachim,Hoppenbrouwers, Fien,Li, Bing-Yu,Van Lommel, Ruben,Verhelst, Steven H. L.,Voets, Lauren
, p. 2270 - 2279 (2022/03/08)
Sulfur(vi) Fluoride Exchange (SuFEx) chemistry has emerged as a next-generation click reaction, designed to assemble functional molecules quickly and modularly. Here, we report the ex situ generation of trifluoromethanesulfonyl fluoride (CF3SO2F) gas in a two chamber system, and its use as a new SuFEx handle to efficiently synthesize triflates and triflamides. This broadly tolerated protocol lends itself to peptide modification or to telescoping into coupling reactions. Moreover, redesigning the SVI-F connector with a SO → SNR replacement furnished the analogous triflimidoyl fluorides as SuFEx electrophiles, which were engaged in the synthesis of rarely reported triflimidate esters. Notably, experiments showed H2O to be the key towards achieving chemoselective trifluoromethanesulfonation of phenols vs. amine groups, a phenomenon best explained - using ab initio metadynamics simulations - by a hydrogen bonded termolecular transition state for the CF3SO2F triflylation of amines. This journal is
A simple route to 1,4-addition reactions by Co-catalyzed reductive coupling of organic tosylates and triflates with activated alkenes
Hsieh, Jen-Chieh,Chu, Yi-Hua,Muralirajan, Krishnamoorthy,Cheng, Chien-Hong
supporting information, p. 11584 - 11587 (2017/10/27)
An efficient Co-catalyzed 1,4-addition reaction of alkyl/aryl triflates and tosylates with activated alkenes is described. In this reaction, an air-stable cobalt(ii) complex, a mild reducing agent Zn and a simple proton source (H2O) are used. A radical mechanism for the addition of alkyl tosylates to activated alkenes is likely involved.
Selective arylation and vinylation at the α position of vinylarenes
Zou, Yinjun,Qin, Liena,Ren, Xinfeng,Lu, Yunpeng,Li, Yongxin,Zhou, Jianrong
supporting information, p. 3504 - 3511 (2013/07/05)
In intermolecular Heck reactions of styrene and vinylarenes, the aryl and vinyl groups routinely insert at the β position. However, selective insertion at the α position has been very rare. Herein, we provide a missing piece in the palette of Heck reaction, which gave >20:1 α selectivity. The key to our success is a new ferrocene 1,1′-bisphosphane (dnpf) that carries 1-naphthyl groups. Our mechanistic studies revealed that the high α selectivity is partly attributable to the steric effect of dnpf. The rigid and bulky 1-naphthyl groups of dnpf sterically disfavor β insertion. What the Heck! In intermolecular Heck reactions, insertion at the β position of aromatic olefins is very common, but reversal of the selectivity for selective α insertion has been a longstanding problem. A general method to couple aryl and vinyl triflates with aromatic olefins in >20:1 α selectivity is presented. The key to this successful approach is a new ferrocene bisphosphane with naphthyl groups on the phosphorus atom (see scheme; OTf=triflate). Copyright
