Palladium acetate-catalyzed cyclization reaction of 2,3-allenoic acids in the presence of simple allenes: an efficient synthesis of 4-(1'-bromoalk-2'(Z)-en-2'-yl)furan-2(5H)-one derivatives and the synthetic application.
We have realized a cyclization reaction of 2,3-allenoic acids 1 in the presence of simple alkyl- or aryl-substituted allenes 3. In this reaction, the cyclic oxypalladation of 2,3-allenoic acid with Pd(II) would afford the furanonyl palladium intermediate 2, which could be trapped by the simple allene to afford a pi-allylic intermediate anti-9. This intermediate anti-9 could be nucleophilically attacked by Br- to yield 4-(1'-bromoalk-2'(Z)-en-2'-yl)furan-2(5H)-one derivatives Z-5 and Pd(0). The in-situ formed Pd(0) was efficiently converted to the catalytically active Pd(II) species by benzoquinone in HOAc. The functional groups, such as malonate, acetoxyl, and phthalic amide in allene 3, are tolerable under the current conditions. High efficiency of chirality transfer was observed when optically active 2,3-allenoic acids were used, which reveals that the formation of the intermediates 2 was a highly stereoselective anti-oxypalladation process. The highly selective formation of Z-isomer may be explained by face-selective coordination of allene 3 with the palladium atom in intermediate 2: the palladium atom coordinates to the terminal C=C double bond of allene 3 from the face opposite to the substituent group to avoid the steric congestion. The products Z-5 could be further elaborated via the S(N)2 nucleophilic substitution with amine or sodium benzenesulfinate, the reduction of the C-Br bond by NaBH(4), and the CuBr.SMe(2)-catalyzed S(N)2'-substitution with CH(3)MgBr.
Gu
Zhenhua
Z
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, People's Republic of China.
Wang
Xinke
X
Shu
Wei
W
Ma
Shengming
S
D000085:Acetates / Q000737:chemistry; D000466:Alkadienes / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D005663:Furans / Q000138:chemical synthesis*; D007783:Lactones / Q000138:chemical synthesis*; D010165:Palladium / Q000737:chemistry
D000085:Acetates; D000466:Alkadienes; D005663:Furans; D007783:Lactones; C025947:propadiene; D010165:Palladium