A New Dirhodium(II) Carboxamidate Complex as a Chiral Lewis Acid Catalyst for Enantioselective Hetero‐Diels–Alder Reactions

Abstract

Over the last decade, the exceptional power of chiral dirhodium(ii) carboxylate and carboxamidate catalysts has been demonstrated in a diverse array of enantioselective metal carbene transformations of diazocarbonyl compounds.[1] Aside from the superiority in diazo decomposition, a dirhodium(ii) complex with vacant coordination sites at the [*] Dr.

Asymmetric syntheses of diarylheptanoid natural products (−)-centrolobine and (−)-de-O-methylcentrolobine via hetero-Diels–Alder reaction catalyzed by dirhodium(II) tetrakis[(R)-3-(benzene-fused-phthalimido)-2-piperidinonate]

“…1). 15,16 In order to demonstrate the utility of this catalytic methodology, we now addressed asymmetric syntheses of (-)-centrolobine (1) and (-)-de-O-methylcentrolobine (2), focusing on the Rh 2 (R-BPTPI) 4 -catalyzed HDA reaction between 4-aryl-2-silyloxy-1,3-butadienes and phenylpropargyl aldehyde derivatives.…”

Catalytic asymmetric hetero-Diels–Alder route to a key intermediate for the synthesis of calyxin L

“…4.87;S,5.95. Found: C,71.23;H,4.88;S,6.04. The enantiomeric excess of 5c was determined to be 91% by HPLC with a Chiralpak AD-H column (1:1 hexane/i-PrOH, 1.0 mL/min); t R (major) = 22.2 min for (2R,6S)-enantiomer; t R (minor) = 34.8 min for (2S,6R)-enantiomer.…”

Chiral Dirhodium(II) Carboxylates: New Insights into the Effect of Ligand Stereo-Purity on Catalyst Structure and Enantioselectivity

“…Their remarkable selectivity has reached a stage where they can function as a powerful tool in building up value added molecules with complex structures [7,[15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34].…”