Stereoselective construction of sterically hindered oxaspirocycles via chiral bidentate directing group-mediated C(sp(3))-O bond formation

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The systematic investigation of chiral bidentate auxiliaries has resulted in the discovery of a chiral 2,2dimethyl- 1-(pyridin-2-yl) propan-1-amine-derived directing group that enables stereoselective palladium(II)-catalyzed intramolecular C(sp(3))-O bond formation. This new chiral directing group exhibited high reactivity in the activation of methylene C(sp(3))-H bonds with excellent levels of stereoselectivity (a diastereomeric ratio of up to 39 : 1), which allowed the construction of a wide range of oxaspirocycles. Mechanistic investigations were also conducted to elucidate the reaction mechanism and understand the origin of the diastereoselectivity. DFT calculations suggest that only modest levels of diastereoselectivity are accomplished at the rate-determining C-H metalation-deprotonation step and the d.r. is further enriched at the reductive elimination step.
Publisher
ROYAL SOC CHEMISTRY
Issue Date
2018-02
Language
English
Article Type
Article
Keywords

C-H BONDS; FORMING REDUCTIVE ELIMINATION; UNACTIVATED C(SP(3))-H; ASYMMETRIC-SYNTHESIS; C(SP(2))-H BONDS; BUILDING-BLOCKS; ETHER SYNTHESIS; DRUG DISCOVERY; METHYL-GROUPS; ARYLATION

Citation

CHEMICAL SCIENCE, v.9, no.6, pp.1473 - 1480

ISSN
2041-6520
DOI
10.1039/c7sc04691j
URI
http://hdl.handle.net/10203/240715
Appears in Collection
CH-Journal Papers(저널논문)
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