147700-76-3

Upstream product

• 147700-75-2 (4S,5S)-2,2-dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanamine 
• 74-88-4 methyl iodide 
• 93379-48-7 (R,R)-TADDOL 
• 147700-73-0 (4R,5R)-4,5-bis[chloro(diphenyl)methyl]-2,2-dimethyl-1,3-dioxolane 
• 74-89-5 methylamine 

Downstream Products

• 1399829-70-9 (3aS,8aS)-hexahydro-2,2,5,7-tetramethyl-4,4,8,8-tetraphenyl-6H-1,3-dioxolo[4,5-e][1,3]diazepin-6-one 

Relevant academic research and scientific papers

Preparation and characterization of new C2- and C 1-symmetric nitrogen, oxygen, phosphorous, and sulfur derivatives and analogs of TADDOL. part II

TADDOL (=α,α,α′,α′-Tetraaryl-1,3- dioxolane-4,5-dimethanol) and the corresponding dichloride are converted to TADDAMINs (=(4S,5S)-2,2,N,N′-tetramethyl-α,α,α′, α′-tetraphenyl-1,3-dioxolan-4,5-dimethanamines) (Scheme 2) and ureas, 12-15, and to TADDOP derivatives with seven-membered O-P-O ester rings (Schemes 3 and 4). Cl/P-Replacement via the Michaelis-Arbuzov reaction (Scheme 7) on mono- and dichlorides, derived from TADDOL, are described. It was not possible to obtain phosphines with the P-atom attached to the benzhydrylic C-atom of the TADDOL skeleton (Schemes 6 and 7). The X-ray crystal structures (Figs. 1 and 2) of ten of the more than 30 new TADDOL derivatives are discussed. Full experimental details are presented. Copyright

Chiral bis(N-sulfonylamino)phosphine- and TADDOL-phosphite-oxazoline ligands: Synthesis and application in asymmetric catalysis

A series of N,P-ligands has been prepared, containing a chiral oxazoline ring and as a second chiral unit a bis(N-sulfonylamino)phosphine group embedded in a diazaphospholidine ring or a cyclic phosphite group derived from TADDOL. These modular ligands are readily synthesized from chiral amino alcohols and chiral 1,2-diamines or TADDOLs. Palladium and iridium complexes derived from these ligands were found to be efficient catalysts for enantioselective allylic alkylation and olefin hydrogenation, respectively.

TADDOLs on their way to late transition metal complexes - synthesis and crystal structure of N- and S-containing TADDOL-derived compounds

As a part of our research program aimed at the synthesis of TADDOL-derived ligands with heteroatoms other than oxygen as chelating units, we describe here new or improved routes to amino TADDOL-analogs (4, 5, 17-19, 21, 22, 26, 34 and 35) and thio-TADDOL-analogs (27-30 and 32).The sulfinato-thiolato Pt-complex 44 was prepared by an oxidative insertion of Pt into the S-S-bond of the corresponding thiosulfinate 29.Furthermore, the X-ray crystal structures of some of the new compounds (2-5, 28, 29, 32, 42 and 44) are presented and discussed. - Keywords: TADDOL derivative; chiral ligand; X-ray structure; platinum complex

Enantioselective aldol and Michael additions of achiral enolates in the presence of chiral lithium amides and amines

It is now well established that lithium enolates and analogous derivatives generally exist as complex structures held together by noncovalent bonds ('supramolecules'). In particular, Li enolates aggregate to give dimers, tetramers, and higher oligomers, whose metal centers may be complexed by solvent molecules or chelating ligands. In addition, the anionoid part of the enolates may hydrogen-bond to weak acids such as secondary amines. Furthermore, such supramolecules can be product-forming species in synthetic reactions of Li enolates. This paper describes our observations of the temporary incorporation of chiral amines or chiral lithium amides into achiral lithium enolate aggregates (an interaction which is simply broken during aqueous workup!) to give enantiomerically enriched products. In particular, enantioselective aldol and Michael additions between achiral enolates and achiral aldehydes or achiral nitroolefins have been achieved in the presence of several chiral amines (or their lithium amides) derived from (S)-valine or (R,R)-tartaric acid. Finally, this report demonstrates the potential usefulness in asymmetric synthesis of ortho lithiation directed by chiral α-aminoalkoxides.

Derivatives of α,α,α′,α′-Tetraaryl-2,2-dimethyl-1,3- Dioxolan-4,5-Dimethanol (TADDOL) containing nitrogen, sulfur, and phosphorus atoms. New ligands and auxiliaries for enantioselective reactions

α,α,α′,α′-Tetraaryl-2,2-dimethyl-l,3 - dioxolan-4,5-dimethanols are converted to bicyclic phosphites and phosphonites (2a-2e) by reaction with Cl2PR and Cl2POR derivatives. - One or both OH groups of the parent TADDOL can be replaced by Cl (→, 4a, 5a), and the halide in turn substituted by azide (→ 4b, 5b), thiocyanide (→ 6), or sulfide (→ 8). Reduction of the azido group(s) to NH2 and N-alkylation or acylation furnishes a variety of amino alcohols (4c-4f) and diamines (5c-5f), as well as a bis(trifluoroacetamide) (5g). Cyclization of the aminoalcohol (4c) produces a bicyclic system (7), containing a pyrrolidine ring (structure determination by X-ray diffraction). - The new chiral compounds containing nitrogen and phosphorus atoms might be useful ligands and auxiliaries for enantioselective syntheses.