The Aza‐Morita–Baylis–Hillman Reaction of N‐Thiophosphoryl Imines Catalyzed by 1,3,5‐Triaza‐7‐phosphaadamantane (PTA) –– Convenient Synthesis of α‐Methylene‐β‐Amino Ketone or Acid Derivatives

Abstract

In the presence of an effective air-stable nucleophilic trialkylphosphane orgaocatalyst, 1,3,5-triaza-7-phosphaadamantane, N-diethoxythiophosphorylimines 1 and N-diphenylthiophosphinoylimines 2 exhibited good reactivity in the methyl vinyl ketone or methyl acrylate based aza-MoritaBaylis-Hillman reaction. The corresponding products were obtained in fair-to-excellent chemical yields. Moreover, the

Application of Primary Allylamines from Morita–Baylis–Hillman Adducts: Cyanogen Azide Mediated Synthesis of Substituted 5‐Aminotetrazoles and Their Attempted Transformation into Tetrazolo[1,5‐a]pyrimidinones

“…The reaction was continued for 2 h at the same temperature and then heated at 90°C for another 3 h, following a literature procedure. [14] Contrary to the reported method, the reaction in our hands was not clean, and TLC analysis displayed a mixture of several nonpolar spots. This led us to seek an alternate route for the synthesis of the 5-aminotetrazole from amine 3a.…”

“…Although Xu et al reported the isolation of such amines as hydrochloride salts through deprotection of aza-MBH adducts prepared from N-dithiophosphoryl imine and activated alkenes, the scope of the methodology was not investigated. [14] Figure 1. MBH acetate as viable precursors to primary allylamines (I and II).…”

Bis(alkynyl) PTA and DAPTA complexes of Pt(II) and Pd(II)

“…The following solvents were purchased from Fisher Chemical Co., distilled over appropriate drying agents under nitrogen prior to use then stored over activated molecular sieves: acetone, chloroform, diethyl ether, ethanol, methanol, methylene chloride, and pentane. Chloroform-d and dimethyl sulfoxide-d 6 were purchased from Cambridge Isotopes Inc. and dried over activated molecular sieves before use. The complex, PtCl 2 (COD) was purchased from Strem Chemical Co. and used as received.…”

“…Transition-metal complexes containing either PTA or DAPTA ligands have been reported for metals of groups 6-12 [3]. Metal-catalyzed reactions involving complexes with the PTA and DAPTA ligands are known for a variety of processes including hydrogenation [4], hydroformylation [4b], hydroamination [5], Aza-Morita-Baylis-Hillman [6], Suzuki [7], and Sonogashira couplings [8], and Baeyer-Villiger oxidation [9] reactions using water as a solvent or an aqueous biphasic solvent system [10]. A significant number of studies on the use of water soluble transition-metal complexes containing the PTA and DAPTA ligands for their medicinal and therapeutic applications are known with numerous studies involving ruthenium systems [3,11].…”

N‐Phosphinyl Imine Chemistry (I): Design and Synthesis of Novel N‐Phosphinyl Imines and their Application to Asymmetric aza‐Henry Reaction

“…In the past several years, we and others have established chiral Nphosphonyl and N-phosphoryl imine chemistry (39)(40)(41)(42)(43)(44)(45)(46)(47)(48)(49)(50) and subsequently applied this chemistry to a series of asymmetric C-C bond formations via carbonyl-type additions including asymmetric catalytic Strecker reaction of achiral N-phosphonyl imines (39,40). These reactions have resulted in versatile chiral amino building blocks in good to excellent chemical yields and diastereo-and enantioselectivities.…”