1015445-13-2Relevant articles and documents
Key factors for high diastereo- And enantioselectivity of umpolung cyclizations of aldehyde-containing allylpalladium intermediates
Tsukamoto, Hirokazu,Kawase, Ayumu,Omura, Hirotaka,Doi, Takayuki
, p. 1743 - 1753 (2019)
Two palladium/chiral diphosphine-catalyzed umpolung cyc-lizations of aldehyde-containing allylic acetates and allenes with arylboronic acid are fully investigated to establish key factors in their high stereoselectivities. Both cyclization reactions afford cis-disubstituted pyrrolidine and tetrahydrofuran. These occur in high diastereo- and enantioselectivities through a common cationic (Z)-η1-allylpalladium, toward which a ring strain generated in the cyclization step leading to trans-isomers biases the equilibrium through η3-η1-η3-complex in the former cyclization. Varied diastereoselectivities were observed in the formation of five-membered carbocycles and six-membered heterocycles. These reflect release of a ring strain generated in the cyclization step leading to trans-isomers and a different distribution of the (Z)- and the (E)-η1-allylpalladium intermediates generated by the oxidative addition of allylic acetates to Pd(0) or carbopalladation of allenes, respectively. A steri-cally demanding substituent at the center of the allyl moiety is necessary for high diastereo- and enantioselectivity. The enantioselectivity of the former cyclization was lowered by the presence of organometallic reductants or reagents, possibly causing the formation of neutral η1-allylpalladium species. We used a chiral allylic acetate containing (E)-deuterium-labeled alkene to demonstrate that the electrophilic attack of the aldehyde to the allyl ligand occurred on the side where the palladium existed, consistent with the Zimmerman-Traxler transition state.
Enantioseiective aryiative cyclization of allenyl aldehydes with arylboronic acids under Pd(II)-diphosphine catalysis
Tsukamoto, Hirokazu,Matsumoto, Tomotaka,Kondo, Yoshinori
supporting information; experimental part, p. 1047 - 1050 (2009/04/06)
A Pd(OAc)2-SEGPHOS combination catalyzes the first enantioseiective aryiative cyclization of allenyl aldehydes with aryiboronic acids to provide c/s-fused fiveand six-membered cyclic homoallylic alcohols. The excellent diastereoand enantioselectivity and the fact that the reaction proceeds at room temperature in the absence of any additives make the process highly practical.
