Magnesium complexes amines

The enantioselective amination of iV-acyl oxazolidinones has been studied as part of a general approach to the synthesis of arylglycines. In this case, the enolization is initiated by a chiral magnesium bis(sulfonamide) complex. The oxazolidinone imide enolates are generated using catalytic conditions (10 mol% of magnesium complex) and treated in situ with BocN=NBoc to provide the corresponding hydrazide. 20 mol% of iV-methyl-p-toluensulfonamide are added to accelerate the reaction (equation 117). 

The catalyzed amination of phenylacetylimide 110a employing the magnesium complex 109 (10 mol%) and A-methyl-p-toluenesulfonamide (20 mol%) in 2 1 CH2C12/Et20 afforded the hydrazide 111a with an enantiomeric ratio (2S) (2R) — 93 7 in 92% yield (Scheme 51, Table 3.11 entry a). 

Itoh and coworkers developed a new route to y-lactams by the ruthenium-catalyzed cyclization of A -allyltrichloroacetamides [132]. Also, Stork and Mah have reported on the radical cyclization ofAT-protected haloacetamides to yield AT-protected lactams. The protecting groups can then be easily removed under a variety of conditions [133]. This efficient radical cyclization route to c -fused pyrrolidones and piperidones is interesting because of the widespread occurrence of related systems in natural products [134]. We have developed a direct method for the one-pot synthesis of y-lactams and secondary amines utilizing conjugated diene-magnesium complexes [135]. 

A second way to improve resolution is the modification of mobility by complexation of the analyte. Many buffers for analysis of cations use HIBA or 18-crown-6 to improve the resolution between sodium, potassium, calcium, magnesium, etc. as well as some aliphatic amines. By diluting an existing validated buffer, one can change the concentration of the complexation agent and thus also the selectivity of the system. 

High yields of amines have also been obtained by reduction of amides with an excess of magnesium aluminum hydride (yield 100%) [577], with lithium trimethoxyaluminohydride at 25° (yield 83%) [94] with sodium bis(2-methoxy-ethoxy)aluminum hydride at 80° (yield 84.5%) [544], with alane in tetra-hydrofuran at 0-25° (isolated yields 46-93%) [994, 1117], with sodium boro-hydride and triethoxyoxonium fluoroborates at room temperature (yields 81-94%) [1121], with sodium borohydride in the presence of acetic or trifluoroacetic acid on refluxing (yields 20-92.5%) [1118], with borane in tetrahydrofuran on refluxing (isolated yields 79-84%) [1119], with borane-dimethyl sulflde complex (5 mol) in tetrahydrofuran on refluxing (isolated yields 37-89%) [1064], and by electrolysis in dilute sulfuric acid at 5° using a lead cathode (yields 63-76%) [1120]. 

Amines such as diethylamine, morpholine, pyridine, and /V, /V, /V, /V -tetramethylethylene-diamine are used to solubilize the metal salt and increase the pH of the reaction system so as to lower the oxidation potential of the phenol reactant. The polymerization does not proceed if one uses an amine that forms an insoluble metal complex. Some copper-amine catalysts are inactivated by hydrolysis via the water formed as a by-product of polymerization. The presence of a desiccant such as anhydrous magnesium sulfate or 4-A molecular sieve in the reaction mixture prevents this inactivation. Polymerization is terminated by sweeping the reaction system with nitrogen and the catalyst is inactivated and removed by using an aqueous chelating agent. 

Failure for Grignard reagents to undergo similar additions to homoallylic amines may be explained by the greater stability of the complexes between an amine and zinc rather than magnesium. By contrast, addition of allylzinc bromide to allyl or homoallyl alcohols proceeded considerably less efficiently compared to amines and the regioselectivity was reversed (equation 55)81. 

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