Addition Reaction Of N-Tosylhydrazones And Synthesis Of Enantioselective Sipro-3,4-DHP-2-Ones

A new metal-free reaction of N-Tosylhydrazones and aryl sulfonyl indoles, which efficient to spiro cyclopropane compounds has been developed in this paper. Under the alkaline conditions, aryl sulfonyl indoles in situ formed N-hetero-dienals intermediates, saturated N-Tosylhydrazones in situ formed saturated diazo compound, The N-hetero-dienals intermediates and diazo compound would proceed to yield a three-membered spiro-indolenines. By sifting the reaction conditions such as base, solvent and temperature to obtain the optimal reaction conditions. With the optimal conditions for the reaction established, the reaction scopes were investigated. Various sulfonyl indoles were compatibled affording the corresponding spiroindolenine in excellent enantioselectivities(4:1-20:1 dr) and good yields(90%-98%). A new method to construct spiro cyclopropane compounds has been developed.A new metal-free reaction of α,β-unsaturated N-Tosylhydrazones and aryl sulfonyl indoles, which efficient to indole compounds with Pyrazole group also has been developed in this paper. Under the alkaline conditions, aryl sulfonyl indoles in situ formed N-hetero-dienals intermediates and α,β-Unsaturated N-Tosylhydrazones in situ formed α,β-Unsaturated diazo then formed Pyrazole intermediate. The Pyrazole intermediate and N-hetero-dienals intermediates would proceed to yield indoles with Pyrazole group via Michael reaction. By sifting the reaction conditions such as base, solvent and temperature to obtain the optimal reaction conditions. With the optimal conditions for the reaction established, the reaction scopes were investigated, various sulfonyl indoles were compatibled affording the corresponding spiroindolenine in good yields(68%-99%). A new method to construct indole compounds with Pyrazole group has been developed.Besides, a reaction of α,β-unsaturated aldehydes and malonamides, which efficient to Spiro-DHP ones has been developed in this paper. In the presence of secondary amine and acid, the α,β-unsaturated aldehydes in situ formed α,β-unsaturated Imines, with a sequential Michael-hemiaminalization-dehydration domino reaction, gained Spiro-DHP-ones. By sifting the reaction conditions such as catalyst, additive, solvent and temperature to obtain the optimal reaction conditions. With the optimal conditions for the reaction established, the reaction scope was investigated, various substrates were compatibled affording the Spiro-DHP ones in excellent enantioselectivities(>18:1 dr, 90%-98% ee) and good yields(57%-99%). A new method to construct spiro-DHP-one compounds has been developed.A Mannich reaction of cyclic N-sulfonylimine and 3-methyl-cyclohex-2- enone has been developed in this paper. In the presence of Primary amine thiourea and acid, the 3-methylcyclohex-2-enone formed dienamine intermediate and following a Mannich reaction of the γ-position of dienamine and N-sulfonylimine. By sifting the reaction conditions such as catalyst, additive, solvent and temperature to obtain the optimal reaction conditions. With the optimal conditions for the reaction established, the reaction scope was investigated, various substrates were compatible in excellent enantioselectivities(89%-99% ee) and good yields(70%-89%). The mannich reaction of cyclic N-sulfonylimine and 3-methy-lcyclohex-2-enone has been systematically studied first time. This part of work is continues to be studied.