Abstract

A novel EtO₂CCF₂-substituted semisquarate is synthesized from diisopropyl squarate by selective 1,2-addition of the Reformatsky reagent derived from BrCF₂CO₂Et and subsequent rhenium-catalyzed allylic alcohol rearrangement. The compatibility of the highly reactive EtO₂CCF₂ group in ring transformations of the obtained semisquarate is investigated. Various EtO₂CCF₂-substituted, highly functionalized compounds, such as quinones, tetronates, cyclopentenones and a bicyclo-[3.2.0]heptenone, are successfully synthesized by ring transformations of the EtO₂CCF₂-substituted semisquarate. Also, an allylO₂CCF₂-substituted semisquarate is prepared and converted into the corresponding tetronate. Subsequent palladium-catalyzed deallylation followed by condensation of the resulting carboxylic acid with several amines under mild conditions affords the corresponding α,α-difluoroamides in good yields.

A novel EtO₂CCF₂-substituted semisquarate is synthesized from diisopropyl squarate by selective 1,2-addition of the Reformatsky reagent derived from BrCF₂CO₂Et and subsequent rhenium-catalyzed allylic alcohol rearrangement. The compatibility of the highly reactive EtO₂CCF₂ group in ring transformations of the obtained semisquarate is investigated. Various EtO₂CCF₂-substituted, highly functionalized compounds, such as quinones, tetronates, cyclopentenones and a bicyclo-[3.2.0]heptenone, are successfully synthesized by ring transformations of the EtO₂CCF₂-substituted semisquarate. Also, an allylO₂CCF₂-substituted semisquarate is prepared and converted into the corresponding tetronate. Subsequent palladium-catalyzed deallylation followed by condensation of the resulting carboxylic acid with several amines under mild conditions affords the corresponding α,α-difluoroamides in good yields.

中文翻译：

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烷氧羰基二氟甲基取代的半方形化合物的合成及其转化

摘要

一种新的EtO ₂ CCF ₂取代的半方酸酯是由二异丙基方酸酯通过选择性地1,2加成源自BrCF ₂ CO ₂ Et的Reformatsky试剂并随后进行-催化的烯丙基醇重排而合成的。研究了高反应性的EtO ₂ CCF ₂基团在所得半方形的环转化中的相容性。各种环氧乙烷₂ CCF ₂ -取代的，高功能的化合物，如醌，tetronates，环戊烯酮和二环- [3.2.0]庚烯酮，成功地由环氧乙烷的环转化合成₂ CCF ₂取代的半方形。同样，制备烯丙基O ₂ CCF ₂取代的半方酸酯，并将其转化为相应的tetronate。随后的钯催化的脱铝反应，然后在温和的条件下将所得的羧酸与几种胺进行缩合，可以以良好的收率得到相应的α，α-二氟酰胺。

一种新的EtO ₂ CCF ₂取代的半方酸酯是由二异丙基方酸酯通过选择性地1,2加成源自BrCF ₂ CO ₂ Et的Reformatsky试剂并随后进行-催化的烯丙基醇重排而合成的。研究了高反应性的EtO ₂ CCF ₂基团在所得半方形的环转化中的相容性。各种环氧乙烷₂ CCF ₂ -取代的，高功能的化合物，如醌，tetronates，环戊烯酮和二环- [3.2.0]庚烯酮，成功地由环氧乙烷的环转化合成₂ CCF ₂取代的半方形。同样，制备烯丙基O ₂ CCF ₂取代的半方酸酯，并将其转化为相应的tetronate。随后的钯催化的脱铝反应，然后在温和的条件下将所得的羧酸与几种胺进行缩合，可以以良好的收率得到相应的α，α-二氟酰胺。