Stereoselective Diboration of Spirocyclobutenes: A Platform for the Synthesis of Spirocycles with Orthogonal Exit Vectors

Nóvoa, Luis; Trulli, Laura; Parra, Alejandro; Tortosa, Mariola

doi:10.1002/ange.202101445

Cited by 16 publications

(2 citation statements)

References 58 publications

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“…The crude residue was then purified by silica flash column chromatography to yield the desired alkene precursor. The literature data for compounds 2m , 2n , 2o , 2p , 2q , 2r , 2t , 2u , 2x , and 2z matched the data obtained using this procedure.…”

Section: Methodssupporting

confidence: 73%

Multicomponent Direct Assembly of N-Heterospirocycles Facilitated by Visible-Light-Driven Photocatalysis

Griffiths

Ley

2022

J. Org. Chem.

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N -heterospirocycles are interesting structural units found in both natural products and medicinal compounds but have relatively few reliable methods for their synthesis. Here, we enlist the photocatalytic generation of N -centered radicals to construct β-spirocyclic pyrrolidines from N -allylsulfonamides and alkenes. A variety of β-spirocyclic pyrrolidines have been constructed, including drug derivatives, in moderate to very good yields. Further derivatization of the products has also been demonstrated as has a viable scale-up procedure, making use of flow chemistry techniques.

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Section: Methodssupporting

confidence: 73%

Multicomponent Direct Assembly of N-Heterospirocycles Facilitated by Visible-Light-Driven Photocatalysis

Griffiths

Ley

2022

J. Org. Chem.

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“…This approach yields 1,2,3‐trisubstituted cyclobutanes that can readily undergo further modifications [8] . The same group also reported asymmetric Pt‐catalyzed diborylation of spirocyclic cyclobutenes [9] and copper‐catalyzed monoboration of spirocyclic cyclobutenes to yield achiral 3‐substituted spirocyclobutanes (Figure 2A). [10] …”

Section: Figurementioning

confidence: 94%

Rhodium‐Catalyzed Asymmetric Arylation of Cyclobutenone Ketals

2023

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Complex cyclobutanes are important motifs in both bioactive molecules and natural products, yet their enantioselective preparation has not been widely explored. In this work, we describe rhodium‐catalyzed enantioselective additions of aryl and vinyl boronic acids to cyclobutenone ketals. This transformation involves enantioselective carbometalation to give cyclobutyl‐rhodium intermediates, followed by β‐oxygen elimination to afford enantioenriched enol ethers. Overall, this addition serves as a surrogate for Rh‐catalyzed 1,4‐additions to cyclobutenone.

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A Modular Access to 1,2‐ and 1,3‐Disubstituted Cyclobutylboronic Esters by Consecutive Radical Additions

2021

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A modular approach to substituted cyclobutylboronic esters is described. It proceeds by successive intermolecular radical additions of xanthates to pinacolato 1‐cyclobutenylboronate and to pinacolato bicyclo[1.1.0]but‐1‐ylboronate. Success hinges on tuning the stability of the α‐boryl radical by exploiting the stabilizing influence of the trivalent boronic ester and the slightly destabilizing cyclobutane, which increases the σ‐character of the radical. Reductive removal of the xanthate group finally provides a range of 1,2‐ and 1,3‐disubstituted cyclobutylboronic esters. The contrast with cyclopropylboronic esters is striking, since the strong destabilization by the highly strained cyclopropane ring allows the first radical addition to take place but not the second. Furthermore, the first adducts are geminal xanthyl boronic esters that can be converted into cyclobutanones. This chemistry furnishes cyclobutylboronic esters that would be quite difficult to obtain otherwise and thus complements existing methods.

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Stereoselective Diboration of Spirocyclobutenes: A Platform for the Synthesis of Spirocycles with Orthogonal Exit Vectors

Cited by 16 publications

References 58 publications

Multicomponent Direct Assembly of N-Heterospirocycles Facilitated by Visible-Light-Driven Photocatalysis

Multicomponent Direct Assembly of N-Heterospirocycles Facilitated by Visible-Light-Driven Photocatalysis

Rhodium‐Catalyzed Asymmetric Arylation of Cyclobutenone Ketals

A Modular Access to 1,2‐ and 1,3‐Disubstituted Cyclobutylboronic Esters by Consecutive Radical Additions

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