Herein we report an efficient stereoselective umpolung 1,2-addition of Et 2 Zn onto α-diketones followed by intramolecular cascade Michael cyclization. This strategy effectively delivers a broad range of substituted 1-indanones in excellent yields in a chemo-and regioselective fashion. Additionally, we performed a variety of synthetic transformations on the 1-indanone products. Furthermore, a hitherto-unexplored asymmetric variant of this methodology that provides up to 94:6 er using an easily accessible cinchona alkaloid ligand has been addressed.

An enantioselective synthesis of Rauhut-Currier (RC) adducts from 3-aryl cyclohexenone with a tethered enone moiety at the ortho-position on the aryl group is accomplished. This method provides a wide range of valuable synthetic building blocks having a unique [6-5-6] all-carbon-fused tricyclic skeleton. A primary amine-containing thiourea, a bifunctional organocatalyst, was found to be an efficient catalyst for this transformation. The primary amine counterpart of the catalyst possibly activates the aliphatic enone via dienamine formation (HOMO activation), whereas the thiourea counterpart activates the tethered enone (LUMO activation). Considering the difficulty in achieving an RC reaction of β,β-disubstituted (alkyl and aryl) enones, this method would be significantly rewarding.

Herein, we disclose a fascinating highly stereoselective P(NMe 2 ) 3 mediated intramolecular deoxygenative umpolung cascade Michael addition-initiated cyclopropanation with a diverse substrate adaptability. This methodology creates a new horizon for expedient access to valuable 6,5,3-fused scaffolds having an all-carbon quaternary stereocenter via Kukhtin−Ramirez (K−R) adduct formation, with excellent diastereoselectivity and yields under metal-free ambient conditions. A few functional group transformations have also been performed successfully. Additionally, an asymmetric catalytic attempt using (R)-(+)-H8-BINOL has delivered good enantioselectivity.

Herein, we unveiled an efficient intramolecular umpolung chemodivergent cascade route for synthesizing 1-indanones via precisely switching the umpolung reactivity between the α-diketone and π-allyl Pd complex. This successful merging of chemodivergent and umpolung strategies is accomplished by employing a Pd catalyst and Et 2 Zn, which provides a broad array of 1indanones with good yield and selectivity. The salient feature involves the amphiphilic behaviors of both α-diketone and allyl functionality in two engineered mild reaction conditions. Furthermore, scale up synthesis and postsynthetic transformations amplify the significance of the current protocol. Additionally, we have achieved the diastereomers of both ether and alcohol derivatives of 1indanone efficiently via synthetic transformation.