The Application Of Novel Cinchona Alkaloids Derived Organocatalysts And The Reaction Of Allenic Ester Catalyzed By Tertiary Phosphines Or Tertiary Amines

This thesis mainly focused on organocatalyzed reactions, and it mainly includes two parts:One is to design novel cinchona alkaloids derived organocatalysts and use them in the catalytic asymmetric substitutions of Morita-Baylis-Hillman adducts and asymmetric [4+2] cycloaddition of allenic esters; the other part is to develop new synthetic reactions of allenic esters catalyzed by tertiary phosphines (phosphites) or tertiary amines, mainly including tertiary phosphines (phosphites) catalyzed cascade reactions of allenic esters with isatins derived oximes and DABCO-catalyzed cyclization of allenic esters with β,γ-unsaturatedα-ketophosphonate orβ,γ-unsaturated a-ketoesters.1 A series of novel cinchona alkaloids derived organocatalysts cat.1-cat.11 have been synthesized and utilized for the asymmetric substitution of O-Boc-protected Morita-Baylis-Hillman adducts with various carbamates and tosylcarbamates, affording the corresponding products in good to high yields and moderate to high ee value (up to 96% ee) under mild conditions.2 Phosphorus-containing Lewis base catalyzed cascade reactions of isatins derived oximes with allenic esters afford the corresponding functionalized nitrones in good yields (72-90% yield), and these nitrones can undergo a highly regioselective intramolecular [3+2] cyclization in the presence of Lewis acid, giving the corresponding bridged cycloadducts in good yields (60-72% yield) under mild conditions. Moreover, a combined "one-pot" synthetic manner is also feasible for above two different catalytic reactions.3 DABCO-catalyzed highly regioselective [4+2] cycloaddition of (3,y-unsaturatedα-ketophosphonate orβ,γ-unsaturated a-ketoesters with allenic ester to give highly functionalized tetrahydropyran and dihydropyran derivatives in good to excellent yields (up to 90% combined yield) under mild conditions.β,γ-unsaturatedα-ketophosphonate as the substrate,Ⅱ-2-3 was afforded as the major product. However,β,γ-unsaturated a-ketoesters as the substrate,Ⅱ-2-7 was afforded as the major product.4 The catalytic abilities of cinchona alkaloids derived catalyst cat.1 -cat. 11 have been examined in the asymmetric [4+2] cycloaddition reaction of salicyl N-tosylimines and allenic esters to give the corresponding chromene adducts in moderate to high yield and moderate to high ee value (up to 87% ee).5 The catalytic asymmetric [4+2] cycloadditions of (3,y-unsaturatedα-ketophosphonates with allenic esters catalyzed by different cinchona alkaloids derived oragnocatalysts have been developed, affording different major product through hydrogen-bonding or pure steric interaction. When we chose cat. 8 as the oragnocatalyst, phosphonates substituted functionalized pyran was afforded in moderate to high yield (65-77% yield) and moderate to high ee value (83-92% ee), and phosphonate substituted functionalized dihydropyran was afforded in moderate to high yield (83-92% yield) and moderate to high ee value (90-96% ee) if use cat. 23 as the oragnocatalyst.6 The catalytic asymmetric [4+2] cycloadditions ofβ,γ-unsaturated oc-ketoesters with allenic esters catalyzed byβ-isocupreidine (P-ICD) has been developed, affording ester-substituented functionalized dihydropyran derivatives in high yields (72-91% yield) along with high enantioselectivities (77-91% ee) under mild conditions.