Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones

Csókás, Dániel; Siitonen, Juha H.; Pihko, Petri M.; Pápai, Imre

doi:10.1021/acs.orglett.0c01008

Publisher's PDF

Katso/Avaa

1.5 Mb

Lataukset:

Show download details Hide download details

Csókás, D., Siitonen, J. H., Pihko, P. M., & Pápai, I. (2020). Conformationally Locked Pyramidality Explains the Diastereoselectivity in the Methylation of trans-Fused Butyrolactones. Organic Letters, 22(12), 4597-4601. https://doi.org/10.1021/acs.orglett.0c01008

Julkaistu sarjassa

Organic Letters

Tekijät

Csókás, Dániel |

Siitonen, Juha H. |

Pihko, Petri M. |

Pápai, Imre

Päivämäärä

2020

Oppiaine

Orgaaninen kemia Organic Chemistry

Tekijänoikeudet

A stereoselectivity model inspired by the total synthesis of stemona alkaloids is developed to explain why enolate-derived 3,4-fused butyrolactones are methylated with a preference for syn alkylation. The model shows how conformational locking present in nonplanar enolate structures favors syn over anti methylation, due to less significant structural distortions in the syn pathway. The developed model was also successfully used to rationalize selectivities of previously documented methylation reactions.

Julkaisija

American Chemical Society

ISSN Hae Julkaisufoorumista

1523-7060

Lisätietoja rahoituksesta

Financial support from the Academy of Finland (project #259532), Jenny and Artturi Wihuri Foundation (research grant to J.H.S.), University of Jyväskylä (postgraduate fellowship to J.H.S), and NKFIH Hungary (grant K-112028) is gratefully acknowledged.

Lisenssi

Ellei muuten mainita, aineiston lisenssi on CC BY 4.0

Näytetään aineistoja, joilla on samankaltainen nimeke tai asiasanat.

5-Carbonyl-1,3-oxazine-2,4-diones from N-Cyanosulfoximines and Meldrum’s Acid Derivatives

Brosge, Felix; Kochs, Johanne,s Florian; Bregu, Mariela; Truong, Khai-Nghi; Rissanen, Kari; Bolm, Carsten (American Chemical Society (ACS), 2020)

At elevated temperatures, N-cyanosulfoximines react with Meldrum’s acid derivatives to give sulfoximines with N-bound 5-carbonyl-1,3-oxazine-2,4-dione groups. A representative product was characterized by single-crystal ...
Design, Construction, and Characterization of a New Regioisomer and Diastereomer Material Based on the Spirooxindole Scaffold Incorporating a Sulphone Function

Al-Majid, Abdullah M.; Soliman, Saied M.; Haukka, Matti; Ali, M.; Islam, Mohammad S.; Shaik, Mohammed R.; Barakat, Assem (MDPI, 2020)

The 1,3-dipolar cycloaddition reaction is one of the most rapid, and efficient protocols to access, and construct highly divergent heterocycle chiral auxiliaries. Free catalyst synthesis of spirooxindole scaffold incorporating ...
Angular Regioselectivity in the Reactions of 2-Thioxopyrimidin-4-ones and Hydrazonoyl Chlorides : Synthesis of Novel Stereoisomeric Octahydro[1,2,4]triazolo[4,3-a]quinazolin-5-ones

Said, Awad I.; Palkó, Márta; Haukka, Matti; Fülöp, Ferenc (MDPI, 2020)

The regioselective synthesis of cis and trans stereoisomers of variously functionalized octahydro[1,2,4]triazolo[4,3-a]quinazolin-5-ones was performed. The 2-thioxopyrimidin-4-ones used in the synthesis reacted with ...
Carboxylate catalyzed isomerization of β,γ‐unsaturated N-acetylcysteamine thioesters

Riuttamäki, Saara; Laszkó, Gergely; Madarász, Ádam; Földes, Tamás; Pápai, Imre; Bannykh, Anton; Pihko, Petri M. (Wiley-VCH Verlag, 2022)

We demonstrate herein the capacity of simple carboxylate salts – tetrametylammonium and tetramethylguanidinium pivalate – to act as catalysts in the isomerization of β,γ-unsaturated thioesters to α,β-unsaturated thioesters. ...
Carboxylate Catalysis : A Catalytic O-Silylative Aldol Reaction of Aldehydes and Ethyl Diazoacetate

Riuttamäki, Saara; Bannykh, Anton; Pihko, Petri M. (American Chemical Society (ACS), 2023)

A mild catalytic variant of the aldol reaction between ethyl diazoacetate and aldehydes is described using a combination of N,O-bis(trimethylsilyl)acetamide and catalytic tetramethylammonium pivalate as catalyst. The ...