228418-79-9Relevant articles and documents
Regio- and stereoselective SN2′ reaction of an allylic picolinate in the synthesis of LY426965
Kobayashi, Yuichi,Yamaguchi, Kai,Morita, Masao
, p. 1826 - 1831 (2018/03/07)
Allylic substitution of secondary γ,γ-disubstituted allylic picolinates with ArMgBr-based copper reagents was applied to the synthesis of LY426965. Reduction of (R)-6-(PMB-oxy)-3-hexyn-2-ol of 93% ee (PMB = p-MeOC6H4CH2) using Red-Al gave (R,Z)-4-iodo-5-(PMB-oxy)hex-3-en-2-ol, which was later converted to the Me-substituted allylic picolinate by Pd-catalyzed coupling with MeZnI followed by esterification with picolinic acid. Allylic substitution with PhMgBr/Cu(acac)2 proceeded with high anti SN2′ selectivity (99%). Ozonolysis, addition of c-Hex-MgBr to the resulting aldehyde, and reductive amination with the piperazine derivative afforded LY426965.
Chiral phosphoramide-catalyzed enantioselective addition of allylic trichlorosilanes to aldehydes. Preparative studies with bidentate phosphorus-based amides
Denmark, Scott E.,Fu, Jiping,Lawler, Michael J.
, p. 1523 - 1536 (2007/10/03)
On the basis of the mechanistic insight that more than one Lewis basic moiety (phosphoramide) is involved in the rate- and stereochemistry-determining step of enantioselective allylation, bidentate chiral phosphoramides were developed. Different chiral phosphoramide moieties were connected by tethers of methylene chains of varying length. The rate and enantioselectivity of allylation with allyltrichlorosilane promoted by the bidentate phosphoramides was found to be highly dependent on the tether length. A new phosphoramide based on a 2,2′-bispyrrolidine skeleton has been designed and afforded good yield, efficient turnover, and high enantioselectivity in allylation reactions. The synthesis of enantiopure 2,2′-bispyrrolidine was easily accomplished on large scale by photodimerization of pyrrolidine followed by resolution with L(or D)-tartaric acid. The scope of the allylation reaction was examined with variously substituted allylic trichlorosilanes and unsaturated aldehydes. This method has been applied to the construction of stereogenic, quaternary centers by the addition of unsymmetrically γ-disubstituted allylic trichlorosilanes.
Enantioselective process for preparing arylated lactones and derivatives
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Page 7-8, (2008/06/13)
This invention provides a process for the arylation of lactones to form to chiral and achiral aryllactones having high enantioselectivity where applicable.