Unveiling the Reaction Mechanism of the Das/Chechik/Marek Synthesis of Stereodefined Quaternary Carbon Centers
Abstract
:1. Introduction
2. Materials and Methods
3. Results
3.1. Formation of Methylcopper(I)
3.2. Carbocupration of the Alkyne Bond
3.3. Analysis of the Regioselectivity of Methyl Transfer
3.4. Homologation of Intermediate 1 with ICH2ZnCH2I
3.4.1. Attack through the Direction Opposite the Oxazolidinone Carbonyl
3.4.2. Attack Proceeding through Zn Coordination by the Oxazolidinone Carbonyl
3.5. Simultaneous Generation of Two Stereocenters through Addition of Aldehyde to Int2
4. Discussion
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
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Reactant State | Transition State | Product | |
---|---|---|---|
Mg moiety | 0.6 | 5.8 | −2.0 |
CuI moiety | 0.0 | −1.0 | 2.2 |
Mg-organic moiety | −2.8 | −21.6 | −4.8 |
CuI-organic moiety | −0.2 | −7.1 | −10.5 |
organic moiety | −0.1 | 1.7 | −10.1 |
Full complex | −3.0 | −17.7 | −10.3 |
Int2 | Int2′ | Int2–Int2′ | |
---|---|---|---|
organic moiety | −348,955.2 | −348,892.7 | −62.5 |
organic moiety + CuI | −478,913.8 | −478,885.5 | −28.3 |
ZnI(CH2I) | −180,031.3 | −180,030.3 | −1.1 |
Full molecule | −659,304.2 | −659,283.0 | −21.3 |
interaction between ZnI(CH2I) and organic-CuI | −359.2 | −367.2 | 8.1 |
Int2 Isoform Reacting with Acetaldehyde | Product Configuration | Activation Free Energy (kcal·mol−1) | C=O∙∙∙∙Zn Distance (Å) | C∙∙∙∙C=O Distance (Å) |
---|---|---|---|---|
Int2α | (S)(S) | 20.2 | 2.07 | 2.29 |
Int2α | (S)(R) | 20.7 | 2.04 | 2.30 |
Int2γ | (S)(S) | 19.8 | 2.02 | 2.06 |
Int2γ | (S)(R) | 18.8 | 2.02 | 2.02 |
Int2β | (R)(R) | 26.9 | 2.04 | 2.25 |
Int2β | (R)(S) | 27.9 | 2.04 | 2.28 |
Int2δ | (R)(R) | 24.9 | 2.05 | 2.32 |
Int2δ | (R)(S) | 23.1 | 2.04 | 2.33 |
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Silva, P.J.; Bernardo, C.E.P. Unveiling the Reaction Mechanism of the Das/Chechik/Marek Synthesis of Stereodefined Quaternary Carbon Centers. Appl. Sci. 2021, 11, 5002. https://doi.org/10.3390/app11115002
Silva PJ, Bernardo CEP. Unveiling the Reaction Mechanism of the Das/Chechik/Marek Synthesis of Stereodefined Quaternary Carbon Centers. Applied Sciences. 2021; 11(11):5002. https://doi.org/10.3390/app11115002
Chicago/Turabian StyleSilva, Pedro J., and Carlos E. P. Bernardo. 2021. "Unveiling the Reaction Mechanism of the Das/Chechik/Marek Synthesis of Stereodefined Quaternary Carbon Centers" Applied Sciences 11, no. 11: 5002. https://doi.org/10.3390/app11115002