Catalytic Asymmetric Sulfa-michael Addition And Asymmetric Cyclization-Mannich Cascade Reaction Of Diazophosphonate

In organic synthesis,the formation of carbon heteroatom bonds is very important,which has aroused the interest of many organic chemists,and developed a number of highly efficient methods for carbon heteroatom bonds construction.Because organic sulfur and nitrogen compounds are widely found in natural and various biological systems,especially in chiral natural products and bioactive molecules,the formation of carbon-sulfur(C-S)and carbon-nitrogen(C-N)bond occupy an important position in the construction of carbon heteroatom bonds.Among them,asymmetric catalysis as an important means of synthesizing chiral compounds is widely used in the synthesis of chiral carbon heteroatom bonds.This thesis described the construction of chiral compounds with carbon-heteroatom bonds forming in the following two parts.Part Ⅰ: The asymmetric sulfa-Michael reaction of thiophenols and nitroolefins has been developed for efficient synthesis of chiral thioethers.This reaction was catalyzed by a chiral multifunctional catalyst.The methodology has the advantages of mild conditions,low catalyst loading(1 mol%),excellent yields(up to 99%)and enantioselectivities(up to 99% ee).Thiophenols,benzyl mercaptans,alkyl thiols as well as mono-substituted and multi-substituted nitroalkenes can take part in this reaction efficiently.This reaction could be scaled up to grams even with a dramatically reduced catalyst loading of 0.05 mol %.Part Ⅱ: Asymmetric cyclization-Mannich cascade reaction of diazophosphonate with aromatic o-alkynyl aldehydes and primary amines has been carried out to synthesize chiral 1,2-dihydroisoquinolines.A series of 3,3’-substituted chiral phosphoric acidsderived from BINOL and SPINOL were designed and synthesized,which,after reacting with silver carbonate in situ,can catalyze this reaction efficiently.Moderate yields and better selectivities can be obtained.