Stereodivergent entry to β-branched β-trifluoromethyl α-amino acid derivatives by sequential catalytic asymmetric reactions

Corti, Vasco; Riccioli, Riccardo; Martinelli, Ada; Sandri, Sergio; Fochi, Mariafrancesca; Bernardi, Luca

doi:10.1039/d1sc01442k

Cited by 20 publications

(2 citation statements)

References 70 publications

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“…Recently, our laboratories reported a conceptually new and stereodivergent approach to β-branched AAs by a sequential process involving the enantioselective transfer hydrogenation of Erlenmeyer–Plöchl substrates followed by the dynamic ring-opening of the resulting azlactones. 146 The realization of this tactic with trifluoromethylated substrates has disclosed a one-pot entry to β-branched, β-trifluoromethyl AA derivatives ( Scheme 51 ). The first step controls the configuration of the β-chirality centre and is performed using an HE and the Jacobsen-type thiourea 55.…”

Section: Manipulation Of the α-Hydrogenmentioning

confidence: 99%

Enantioselective organocatalytic strategies to access noncanonical α-amino acids

Pecchini,

Fochi,

Bartoccini

et al. 2024

Chem. Sci.

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Section: Manipulation Of the α-Hydrogenmentioning

confidence: 99%

Enantioselective organocatalytic strategies to access noncanonical α-amino acids

Pecchini,

Fochi,

Bartoccini

et al. 2024

Chem. Sci.

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“…The intrinsic diastereomeric relationship between the transitions states leading to the cis - 8aa and to the trans - 8aa isomer justifies the requirement of different (i.e., not enantiomeric) catalytic structures for the two reactions (see the Supporting Information ). 20 …”

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confidence: 99%

Sulfoxonium Ylides in Aminocatalysis: An Enantioselective Entry to Cyclopropane-Fused Chromanol Structures

et al. 2022

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The 1,1a,2,7b-tetrahydrocyclopropa[ c ]chromene, arising from fusion of chromane and cyclopropane rings is the core of medicinally relevant compounds. Engaging sulfoxonium ylides in enantioselective aminocatalytic reactions for the first time, a convenient entry to this scaffold is presented. Several ring-fused derivatives were obtained in moderate-to-good yields and enantioselectivities and with perfect diastereoselectivity at the cyclopropane, using an α,α-diphenylprolinol aminocatalyst. The versatility of the hemiacetal moiety in the products was leveraged to effect various synthetic manipulations.

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Stereodivergent Synthesis of Chiral Hydrobenzofuranpyrrolidines by Catalytic Asymmetric Dearomative Cyclization and Controlled Epimerization

Liu,

Huang,

Dai

et al. 2024

Adv Synth Catal

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A methodology to access stereoisomeric sets of products bearing multiple stereogenic centers is still a significant challenge in asymmetric catalysis. We present herein our experimental studies on the stereodivergent synthesis of chiral hydrobenzofuran‐fused pyrrolidines with three stereogenic centers via organocatalytic asymmetric dearomative cyclization and epimerization process. Chiral bifunctional thiourea catalyst could successfully promote the enantioselective dearomatization cyclization of 2‐nitrobenzofurans with o‐hydroxy aromatic aldimines, which enabled the synthesis of (3S,3aR,8bR)‐hydrobenzofuran[3.2]pyrrolidines in 79–92% yields with >20:1 stereoselectivities and 93–>99% enantio‐selectivities. While catalytic amount of DBU could induce the direct intramolecular epimerization of (3S,3aR,8bR)‐hydrobenzofuran[3.2] pyrrolidines to its diastereomers (3R,3aR,8bR)‐hydrobenzofuran[3.2] pyrrolidines in 72–87% yields without loss of stereoselectivities. The mechanistic pathways of the epimerization process were investigated by a series of control experiments study. This work provides an alternative and forward solution for the stereodivergent preparation of functionalized pyrrolidines with potential bioactivities.

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Stereodivergent entry to β-branched β-trifluoromethyl α-amino acid derivatives by sequential catalytic asymmetric reactions

Abstract: Currently, conventional reductive catalytic methodologies do not guarantee general access to enantioenriched β-branched β-trifluoromethyl α-amino acid derivatives. Herein, a one-pot approach to these important α-amino acids, grounded on the reduction...

Cited by 20 publications

References 70 publications

Enantioselective organocatalytic strategies to access noncanonical α-amino acids

Enantioselective organocatalytic strategies to access noncanonical α-amino acids

Sulfoxonium Ylides in Aminocatalysis: An Enantioselective Entry to Cyclopropane-Fused Chromanol Structures

Stereodivergent Synthesis of Chiral Hydrobenzofuranpyrrolidines by Catalytic Asymmetric Dearomative Cyclization and Controlled Epimerization

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