217446-36-1Relevant academic research and scientific papers
Isothiourea-catalyzed enantioselective carboxy group transfer
Joannesse, Caroline,Johnston, Craig P.,Concellon, Carmen,Simal, Carmen,Philp, Douglas,Smith, Andrew D.
, p. 8914 - 8918 (2009)
Transferable skills: Enantiomerically pure isothioureas promote the 0-to C-carboxyl group transfer of oxazolyl carbonates with excellent levels of enantiocontrol (see scheme). The origin of the enantioselectivity of this process was probed mechanistically and rationalized computationally.
Enantioselective TADMAP-catalyzed carboxyl migration reactions for the synthesis of stereogenic quaternary carbon
Shaw, Scott A.,Aleman, Pedro,Christy, Justin,Kampf, Jeff W.,Va, Porino,Vedejs, Edwin
, p. 925 - 934 (2007/10/03)
The chiral, nucleophilic catalyst TADMAP [1, 3-(2,2,2-triphenyl-1- acetoxyethyl)-4-(dimethylamino)-pyridine] has been prepared from 3-lithio-4-(dimethylamino)pyridine (5) and triphenylacetaldehyde (3), followed by acylation and resolution. TADMAP catalyzes the carboxyl migration of oxazolyl, furanyl, and benzofuranyl enol carbonates with good to excellent levels of enantioselection. The oxazole reactions are especially efficient and are used to prepare chiral lactams (23) and lactones (30) containing a quaternary asymmetric carbon. TADMAP-catalyzed carboxyl migrations in the indole series are relatively slow and proceed with inconsistent enantioselectivity. Modeling studies (B3LYP/6-31G*) have been used in qualitative correlations of catalyst conformation, reactivity, and enantioselectivity.
Development of Chiral Nucleophilic Pyridine Catalysts: Applications in Asymmetric Quaternary Carbon Synthesis
Shaw, Scott A.,Aleman, Pedro,Vedejs, Edwin
, p. 13368 - 13369 (2007/10/03)
TADMAP (1a), a new chiral DMAP catalyst, has been designed to place a C(3)-benzylic trityl group over one face of the pyridine ring, while a C(3)-benzylic acetoxy group creates a chirotopic environment on the other face. TADMAP was prepared in four steps
