Additive Reaction Of Carbamoylsilane With α-ketoesters And Synthesis Of Chiral α-aminoamide

This paper studies two reactions. The synthesis of N,N-dim-ethyl(trimethylsilyl)formamide2and N-(methoxymethyl)-N-methyl-(trimethylsilyl)formamide3, The reaction of N,N-dimethyl(trimet-hylsilyl)formamide2with glyoxylic acid ethyl ester compounds,The reaction of N-(methoxymethyl)-N-methyl(trimethylsilyl)forma-mide3with glyoxylic acid ethyl ester compounds, The reaction-n of N,N-dimethyl(trimethylsilyl)formamide2with arylglyoxylate-s menthol esters; Synthesis of chiral α-aminoamide.N,N-dimethyl(trimethylsilyl)formamide2was used to react ofPhenyl gyoxilic acid ethyl ester4, Methyl phenylglyoxylic acidethyl ester5, Methoxy phenyl glyoxilic acid ethyl ester6,2-met-hyl-5-phenyl isopropyl acetonic acid ethyl ester7, Fluorine phen-yl glyoxilic acid ethyl ester of8, Ethyl phenyl glyoxilic acid chlo-ride to9, The bromo phenyl gyoxilic ethyl ester10,2-furyl ac-etonic acid ethyl ester11,2-thiophene glyoxylate ethyl ester12, Ethyl pyruvate13, Styryl acetonic acid ethyl ester14, to afford2-ethoxy-N,N-dimethyl-2-phenyl-2-(trimethylsilyloxy)acetamide15,2-ethoxy-N,N-dimethyl-2-p-tolyl-2-(trimethylsilyloxy)acetamide16,2-ethoxy-2-(4-methoxyphenyl)-N,N-dimethyl-2-(trimethylsilyloxy)acetamide17,2-ethoxy-2-(5-isopropyl-2-methylphenyl)-N,N-dimethyl-2-(trimethylsilyloxy)acetamide18,2-ethoxy-2-(4-fluorophenyl)-N,N- dimethyl-2-(trimethylsilyloxy)acetamide19,2-(4-chlorophenyl)-2-et-hoxy-N,N-dimethyl-2-(trimethylsilyloxy)acetamide20,2-(4-bromop-henyl)-2-ethoxy-N,N-dimethyl-2-(trimethylsilyloxy)acetamide21,2-ethoxy-2-(furan-2-yl)-N,N-dimethyl-2-(trimethylsilyloxy)acetamide22,2-ethoxy-N,N-dimethyl-2-(thiophen-2-yl)-2-(trimethylsilyloxy)ac-etamide23, ethyl-3-(dimethylamino)-2-methyl-3-oxo-2-(trimethylsil-yloxy)propanoate24,(E)-ethyl-2-(dimethylcarbamoyl)-4-phenyl-2-(trimethylsilyloxy)but-3-enoate25, experimental results show th-at ethyl pyruvate13and Carbamoylsilane2reaction yield waslower, due to ortho methyl ethyl pyruvate steric effects andthe hydrolysis of alpha hydrogen decomposition of Carbamoylsil-ane2. Aromatic α-ketoesters reaction, benzene ring is connect-ed with electron donating groups, short reaction time, high yiel-d. When connected with electron rich groups furyl, thiophene,can also react. Even with a styrene group, short reaction time,high yield.Carbamoylsilane3was used to react of Phenyl gyoxilic a-cid ethyl ester4, Methyl phenylglyoxylic acid ethyl ester5, Me-thoxy phenyl glyoxilic acid ethyl ester6,2-methyl-5-phenyl isopr-opyl acetonic acid ethyl ester7, Fluorine phenyl glyoxilic acid ethyl ester of8, Ethyl phenyl glyoxilic acid chloride to9, The bromo phenyl gyoxilic ethyl ester10,2-furyl acetonic acid ethy-lester11,2-thiophene glyoxylate ethyl ester12, Ethyl pyruvate13,Styryl acetonic acid ethyl ester14, to afford2-ethoxy-N-(m-ethoxymethyl)-N-methyl-2-phenyl-2-(trimethylsilyloxy)acetamide26,2-ethoxy-N-(methoxymethyl)-N-methyl-2-p-tolyl-2-(trimethylsily-loxy)acetamide27,2-ethoxy-N-(methoxymethyl)-2-(4-methoxyphe-nyl)- N-methyl-2-(trimethylsilyloxy)acetamide28,2-ethoxy-2-(5-iso-propyl-2-methylphenyl)-N-(methoxymethyl)-N-methyl-2-(trimethylsil-yloxy)acetamide29,2-ethoxy-2-(4-fluorophenyl)-N-(methoxymethyl)-N-methyl-2-(trimethylsilyloxy)acetamide30,2-(4-chlorophenyl)-2-ethoxy-N-(methoxymethyl)-N-methyl-2-(trimethylsilyloxy)acetamide31,2-(4-bromophenyl)-2-ethoxy-N-(methoxymethyl)-N-methyl-2-(tr-imethylsilyloxy)acetamide32,2-ethoxy-2-(furan-2-yl)-N-(methoxy-methyl)-N-methyl-2-(trimethylsilyloxy)acetamide33,2-ethoxy-N-(methoxymethyl)-N-methyl-2-(thiophen-2-yl)-2-(trimethylsilyloxy)ac-etamide34,(E)-2-ethoxy-N-(methoxymethyl)-N-methyl-4-phenyl-2-(trimethylsilyloxy)but-3-enamide35, experimental results show that aromatic α-ketoesters reaction, benzene ring is connected with electron donating groups, short reaction time, high yield. When connected with electron rich groups furyl, thiophene, canalso react. Even with a styrene group, short reaction time, highyield.Carbamoylsilane2was used to react of2-isopropyl-5-methy-lcyclohexyl2-oxo-2-phenylacetate﹑2-isopropyl-5-methylcyclohex-yl2-(4-methoxyphenyl)-2-oxoacetate2-isopropyl-5-methylcyclohe-xyl2-(5-isopropyl-2-methylphenyl)-2-oxoacetate﹑2-isopropyl-5-me-thylcyclohexyl2-(4-fluorophenyl)-2-oxoacetate﹑2-isopropyl-5-met-hylcyclohexyl2-(4-chlorophenyl)-2-oxoacetate﹑2-isopropyl-5-met-hylcyclohexyl2-(4-bromophenyl)-2-oxoacetate to afford2-isopro-pyl-5-methylcyclohexyl3-(dimethylamino)-3-oxo-2-phenyl-2-(trimet-hylsilyloxy)propanoate﹑2-isopropyl-5-methylcyclohexyl3-(dimeth-ylamino)-2-(4-methoxyphenyl)-3-oxo-2-(trimethylsilyloxy)propanoat-e﹑2-isopropyl-5-methylcyclohexyl3-(dimethylamino)-2-(5-isopropy-l-2-methylphenyl)-3-oxo-2-(trimethylsilyloxy)propanoate﹑2-isoprop- yl-5-methylcyclohexyl3-(dimethylamino)-2-(4-fluorophenyl)-3-oxo-2-(trimethylsilyloxy)propanoate﹑2-isopropyl-5-methylcyclohexyl2-(4-chlorophenyl)-3-(dimethylamino)-3-oxo-2-(trimethylsilyloxy)prop-anoate﹑2-isopropyl-5-methylcyclohexyl2-(4-bromophenyl)-3-(dim-ethylamino)-3-oxo-2-(trimethylsilyloxy)propanoate experimental r-esults show that Carbamoylsilane2and menthyl arylglyoxylatesstrong reactive activity, high activity. But the stereoselectivityis not strong.Carbamoylsilane2was used to react of ethyl3-nitrobenzoate﹑ethyl4-nitrobenzoate, To generate the corresponding interme-diate ketal, ketal unstable under acidic conditions, Acidic cond-itions the decomposition of the corresponding N,N-dimethyl-2-(4-nitrophenyl)-2-oxoacetamide76, N,N-dimethyl-2-(3-nitrophenyl)-2-oxoacetamide77. Comparison of Carbamoylsilane2with aldehy-de and ketone reaction, the reaction activity of Carbamoylsilan-e with ester yield is low, low.α-aminoamide.α-ketoesters49,50,51,52,53,54,55,56Respectively with(S)-2-methylpropane-2-sulfinamide and (R)-2-methylpropane-2-sulf-inamide to afford (S,E)-N,N-dimethyl-2-(2-methylpropan-2-ylsulfin-amido)-2-phenylacetamide57,(R,E)-N,N-dimethyl-2-(2-methylprop-an-2-ylsulfinamido)-2-phenylacetamide58,(S,E)-N,N-dimethyl-2-(2-methylpropan-2-ylsulfinamido)-2-p-tolylacetamide59,(R,E)-N,N-di-methy-l-2-(2-methylpropan-2-ylsulfinamido)-2-p-tolylacetamide60,(S,E)-N,N-dimethyl-2-(2-methylpropan-2-ylsulfinamido)-2-o-tolylace-tamide61,(R,E)-N,N-dimethyl-2-(2-methylpropan-2-ylsulfinamido)-2-o-tolylace-tamide62,(S,E)-2-(3-methoxyphenyl)-N,N-dimethyl-2-(2-methylpropa-n-2-ylsulfinamido)acetamide63,(R,E)-2-(3-methox- yphenyl)-N,N-dimethyl-2-(2-methylpropan-2-ylsulfinamido)acetamid-e64,(S,E)-N,N-dimethyl-2-(2-methylpropan-2-ylsulfinamido)-2-(4-ni-trophenyl)acetamide65,(R,E)-N,N-dimethyl-2-(2-methylpropan-2-y-lsulfinamido)-2-(4-nitrophenyl)acetamide66,(2E,3E)-N,N-dimethyl-2-((S)-2-methylpropan-2-ylsulfinamido)-4-phenylbut-3-enamide67,(2E,3E)-N,N-dimethyl-2-((R)-2-methylpropan-2-ylsulfinamido)-4-phe-nylbut-3-enamide68,(S,E)-2-(furan-2-yl)-N,N-dimethyl-2-(2-methyl-propan-2-ylsulfinamido)acetamide69,(R,E)-2-(furan-2-yl)-N,N-dim-ethyl-2-(2-methylpropan-2-ylsulfinamido)acetamide70,(S,Z)-N,N-dimethyl-2-(2-methylpropan-2-ylsulfinamido)-2-(thiophen-2-yl)aceta-mide71,(R,Z)-N,N-dimethyl-2-(2-methylpropan-2-ylsulfinamido)-2-(thiophen-2-yl)acetamide72. experimental results show that Wh-en alpha bit connected with electron withdrawing groups strong,strong reactive activity, short reaction time, high yield.(R,E)-N,N-dimethyl-2-(2-methylpropan-2-ylsulfinamido)-2-p-tolylacetamide60reduction to generate(R)-N,N-dimethyl-2-((R)-2-methylpropan-2-ylsulfinamido)-2-p-tolylacetamide, Reducing age-nt corresponding to a high selectivity.