211303-82-1Relevant academic research and scientific papers
Enantioselective Synthesis of α-Allyl Amino Esters via Hydrogen-Bond-Donor Catalysis
Bendelsmith, Andrew J.,Kim, Seohyun Chris,Wasa, Masayuki,Roche, Stéphane P.,Jacobsen, Eric N.
supporting information, p. 11414 - 11419 (2019/08/20)
We report a chiral-squaramide-catalyzed enantio- and diastereoselective synthesis of α-allyl amino esters. The optimized protocol provides access to N-carbamoyl-protected amino esters via nucleophilic allylation of readily accessible α-chloro glycinates. A variety of useful α-allyl amino esters were prepared, including crotylated products bearing vicinal stereocenters that are inaccessible through enolate alkylation, with high enantioselectivity (up to 97% ee) and diastereoselectivity (>10:1). The reactions display first-order kinetic dependence on both the α-chloro glycinate and the nucleophile, consistent with rate-limiting C-C bond formation. Computational analysis of the uncatalyzed reaction predicts an energetically inaccessible iminium intermediate, and a lower energy concerted SN2 mechanism.
Pd-Catalyzed C(sp3)-C(sp2) cross-coupling of Y(CH2SiMe3)3(THF)2 with vinyl bromides and triflates
Cai, Guilong,Zhou, Zhibing,Wu, Wenchao,Yao, Bo,Zhang, Shaowen,Li, Xiaofang
, p. 8702 - 8706 (2016/10/03)
Pd-Catalyzed C(sp3)-C(sp2) cross-coupling of Y(CH2SiMe3)3(THF)2 with vinyl bromides and triflates has been developed for efficient synthesis of various allyltrimethylsilanes. The cross-coupling reaction was conducted at room temperature with low catalyst loading of either Pd(PPh3)4 or Pd(PPh3)2Cl2, and exhibited high efficiency and a broad substrate scope. In combination with the cross-coupling by the Lewis-acid catalyzed Hosomi-Sakurai reaction, a novel three-component one-pot cascade reaction was then accomplished to deliver homoallylic alcohols and ethers with high regioselectivity and diastereoselectivity. The three-component reaction defined the yttrium complex as a novel one-carbon synthon, which could either trigger bifunctionalization of alkenes or link two electrophiles and would find applications in organic synthesis.
Copper-catalyzed trifluoromethylation of allylsilanes
Shimizu, Ryo,Egami, Hiromichi,Hamashima, Yoshitaka,Sodeoka, Mikiko
supporting information; experimental part, p. 4577 - 4580 (2012/06/18)
CF3 on Csp3: Trifluoromethylation of allylsilane derivatives was accomplished through the use of CuI and Togni's reagent (1) under mild conditions. The reaction of allylsilanes without a substituent in the 2-position gave vinylsilane derivative
Highly Regioselective Palladium-Catalyzed Internal Arylation of Allyltrimethylsilane with Aryl Triflates
Olofsson, Kristofer,Larhed, Mats,Hallberg, Anders
, p. 5076 - 5079 (2007/10/03)
Highly regioselective ligand-controlled Heck-arylation reactions of allyltrimethylsilane, delivering branched β-products, were performed in moderate to good yields. The high preference for internal over terminal double-bond arylation suggests a contributi
