A Stereoselective Hydride Transfer Reaction With Contributions From Attractive Dispersion Force Control
DOI: 10.14469/hpc/9237 Metadata
Created: 2021-10-08 08:49
Last modified: 2022-04-07 19:45
License: Creative Commons: Public Domain Dedication 1.0
Funding: (none given)
Co-author: D. Christopher Braddock Co-author: Krzysztof Oliwa Co-author: Natnicha Limpaitoon
Description
Recently, we reported the addition of the lithium acetylide of alkyne 1 to adamantane carboxaldehyde 2 unexpectedly produced quantities of ynone 3 and adamantane methanol 4 (Figure 1).1 We invoked a hydride transfer in a six-membered chair-like transition state (TS A) from the initially formed secondary lithium alkoxide AdCH(C≡CtBu)OLi to still unreacted AdCHO to explain this observation. In line with this explanation, isolation of the expected addition product 5, and reformation of the lithium alkoxide in the presence of AdCHO 2 gave the same products.1 While the transfer of hydride from LiCCH (e.g., tBuLi)2 and LiNCH (e.g., LDA)3 motifs to carbonyl compounds are well precedented, to the best of our knowledge the above example constitutes the only known example of hydride transfer from a LiOCH atomic tetrad to a carbonyl compound.§ We noted that this outcome could be linked to the particular structure of this secondary alkoxide whereby steric compression of the adamantyl bearing sp3 centre is simultaneously relieved as the formation of conjugated ynone 3 acts as a thermodynamic driving force. While these two factors seem intuitive to the organic chemist, and where we invoked TS A with the adamantyl groups of both components in equatorial positions, herein we provide computational and experimental evidence for a third factor at work: attractive dispersion forces that help stabilise a transition state with the adamantyl grouping of the aldehyde occupying an axial position (TS B).
Members
| DOI | Description |
|---|---|
| 10.14469/hpc/9238 | Computational data for transition state models for a Stereoselective Hydride Transfer Reaction with contributions from Attractive Dispersion Force Control |
| 10.14469/hpc/9240 | NMR, IR and MS spectroscopic data for a Stereoselective Hydride Transfer Reaction With Contributions From Attractive Dispersion Force Control |
| 10.14469/hpc/9239 | Computational and experimental data for Vibrational circular dichroism (VCD) analysis for a Stereoselective Hydride Transfer Reaction With Contributions From Attractive Dispersion Force Control |
| 10.14469/hpc/9241 | Crystallographic data for a Stereoselective Hydride Transfer Reaction with Contributions from Attractive Dispersion Force Control. |
Associated DOIs
| Current dataset ... | DOI | Description |
|---|---|---|
| References | 10.1039/C6CC06395K | Article: Stable bromoallene oxides Stable bromoallene oxides Stable bromoallene oxides Stable Bromoallene oxides |
| isReferencedBy | 10.1039/D2CC01136K | Published article: A stereoselective hydride transfer reaction with contributions from attractive dispersion force control |
| References | 10.14469/hpc/8046 | Student project report: Computational study of intermolecular hydride transfer from bulky lithium propargyl alkoxides to aldehydes |