Role of Noncovalent Interactions in Inducing High Enantioselectivity in an Alcohol Reductive Deoxygenation Reaction Involving a Planar Carbocationic Intermediate
Bibliographic record
Abstract
The involvement of planar carbocation intermediates is generally considered undesirable in asymmetric catalysis due to the difficulty in gaining facial control and their intrinsic stability issues. Recently, suitably designed chiral catalyst(s) have enabled a guided approach of nucleophiles to one of the prochiral faces of carbocations affording high enantiocontrol. Herein, we present the vital mechanistic insights from our comprehensive density functional theory (B3LYP-D3) study on a chiral Ir-phosphoramidite-catalyzed asymmetric reductive deoxygenation of racemic tertiary α-substituted allenylic alcohols. The catalytic transformation relies on the synergistic action of a phosphoramidite-modified Ir catalyst and Bi(OTf) 3, first leading to the formation of an Ir-π-allenyl carbocation intermediate through a turn-over-determining S N 1 ionization, followed by a face-selective hydride transfer from a Hantzsch ester analogue to yield an enantioenriched product. Bi(OTf) 3 was found to promote a significant number of ionic interactions as well as noncovalent interactions (NCIs) with the catalyst and the substrates (allenylic alcohol and Hantzsch ester), thus providing access to a lower energy route as compared to the pathways devoid of Bi(OTf) 3 . In the nucleophilic addition, the chiral induction was found to depend on the number and efficacy of such key NCIs. The curious case of reversal of enantioselectivity, when the α-substituent of the allenyl alcohol is changed from methyl to cyclopropyl, was identified to originate from a change in mechanism from an enantioconvergent pathway (α-methyl) to a dynamic kinetic asymmetric transformation (α-cyclopropyl). These molecular insights could lead to newer strategies to tame tertiary carbocations in enantioselective reactions using suitable combinations of catalysts and additives.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.002 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".