Quaternary heteroatom containing compounds

A method comprising

• treating a compound of Formula (III):
• with a transition metal catalyst under alkylation conditions, thereby preparing a compound of Formula (IV):
• wherein the compound of Formula (IV) comprises one of a (+) enantiomer or a (−) enantiomer in an enantiomeric excess of greater than 50%,
• wherein the transition metal catalyst is selected from Mo(CO)6, Mo(MeCN)3(CO)3, W(CO)6, W(MeCN)3(CO)3, [Ir-(1,5-cyclooctadiene)Cl]2, [Ir(1,5-cyclooctadiene)Cl]2, [Ir(1,5-cyclooctadiene)Cl]2, Rh(PPh3)3Cl, [Rh(1,5-cyclooctadiene)Cl]2, Ru(pentamethylcyclopentadienyl)(MeCN)3PF6, Ni(1,5-cyclooctadiene)2, Ni[P(OEt)3]4, tris(dibenzylideneacetone)dipalladium(0), tris(dibenzylideneacetone)dipalladium(0)-chloroform adduct, bis(4-methoxybenzylidene)acetone)dipalladium(0), Pd(OC(═O)CH3)2, Pd(3,5-dimethyoxy-dibenzylideneacetone)2, PdCl2(R23CN)2;
• PdCl2(PR24R25R26)2;
• [Pd(η3-allyl)Cl]2;
• and Pd(PR24R25R26)4, whrein R23, R24, R25, and R26 are independently selected from H, alkyl, alkenyl, alkynyl, carbocycle, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, allylchloro[1,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]palladium(II-), ([2S, 3S]-bis[diphenylphosphino]butane)(η3-allyl)palladium(II) perchlorate, [S]-4-tert-butyl-2-(2-diphenylphosphanyl-phenyl)-4,5-dihydro-oxazole(η-3-allyl)palladium(II) hexafluorophosphate, [Pd(S-tBu-PHOX)(allyl)]PF6, and cyclopentadienyl(η3-allyl) palladium(II);
• wherein, as valence and stability permit,
• X is selected from NR6— and —O—;
• Z is selected from —C(O)— and CR7R7—;
• A is independently selected at each occurrence from —CR8R8— and —NR9—;
• W is absent or selected from —O—, —NR10—, and —CR11R11—;
• R1 is selected from optionally substituted alkyl, alkenyl, alkynyl, carbocyclyl, heterocycle, aryl, heteroaryl, and halogen;
• R2, R3, R4, R5, R12, R13, R14, and R15 are independently selected at each occurrence from hydrogen, hydroxyl, halogen, nitro, alkyl, alkenyl, alkynyl, cyano, carboxyl, sulfate, amino, alkoxy, alkylamino, alkylthio, hydroxyalkyl, alkoxyalkyl, aminoalkyl, thioalkyl, ether, thioether, ester, amide, thioester, carbonate, carbamate, urea, sulfonate, sulfone, sulfoxide, sulfonamide, acyl, acyloxy, acylamino, aryl, heteroaryl, carbocyclyl, heterocyclyl, aralkyl, aralkyloxy, hetaralkyl, carbocyclylalkyl, and heterocyclylalkyl;
• R7, R8, and R11 are independently selected at each occurrence from hydrogen, halogen, nitro, alkyl, alkenyl, alkynyl, cyano, hydroxyl, thiol, carboxyl, sulfate, amino, alkoxy, alkylamino, alkylthio, hydroxyalkyl, alkoxyalkyl, aminoalkyl, thioalkyl, ether, thioether, ester, amide, thioester, carbonate, carbamate, urea, sulfonate, sulfone, sulfoxide, sulfonamide, acyl, acyloxy, acylamino, aryl, heteroaryl, carbocyclyl, heterocyclyl, aralkyl, aralkyloxy, hetaralkyl, carbocyclylalkyl, and heterocyclylalkyl;
• wherein R7 and R8 may combine with the carbons to which they are bound to form an optionally substituted 3-8-membered ring, R8 and R11 may combine with the carbons to which they are bound to form an optionally substituted 3-8-membered ring, and when n is 2 or 3, R8 attached to one carbon may combine with R8 attached to another carbon to combine with the carbons to which they are bound to form a 3-8-membered ring;
• R6, R9 and R10 are independently selected at each occurrence from hydrogen, hydroxyl and optionally substituted alkyl, alkoxy, alkylthio, aryloxy, carbocyclyl, aryl, heteroaryl, aralkyl, heteroaralkyl, aralkyloxy, heteroaryloxy, acyl, arylcarbonyl, aralkylcarbonyl, acyloxy, sulfone, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, and amide;
• and
• n is 0-3.