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Record W2018628410 · doi:10.1002/hlca.200490205

Regio‐ and Stereoselective 1,3‐Oxathiolane Formation in the Reaction of Thiolactones with Optically Active Oxiranes

2004· article· en· W2018628410 on OpenAlex

Why this work is in the frame

A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.

affAt least one author lists a Canadian institution in the pinned OpenAlex snapshot.

Bibliographic record

VenueHelvetica Chimica Acta · 2004
Typearticle
Languageen
FieldChemistry
TopicOrganic Chemistry Cycloaddition Reactions
Canadian institutionsInstitute of Particle Physics
Fundersnot available
KeywordsChemistryIsobenzofuranRing (chemistry)NucleophileStereoselectivityOptically activeStereochemistryAnhydrousMedicinal chemistryOrganic chemistryCatalysis

Abstract

fetched live from OpenAlex

Abstract The reactions of 3 H ‐isobenzofuran‐1‐thione ( 1 ) with ( S )‐2‐methyloxirane ( 2 ) and ( R )‐2‐phenyloxirane ( 6 ) in the presence of SiO 2 in anhydrous CH 2 Cl 2 led to two pairs of diastereoisomeric spirocyclic 1,3‐oxathiolanes, i.e. , 3 and 4 with a Me group at C(5′), and 7 and 8 with a Ph group at C(4′), respectively ( Schemes 2 and 3 ). In both cases, 3 H ‐isobenzofuran‐1‐one ( 5 ) was formed as a main product. The analogous reactions of 3,4‐dihydro‐2 H‐ [1]benzopyran‐2‐thione ( 9 ) and 3,4,5,6‐tetrahydro‐2 H ‐pyran‐2‐thione ( 14 ) with 2 and 6 yielded four pairs of the corresponding diastereoisomeric spirocyclic compounds 10 and 11, 12 and 13, 15 and 16 , and 18 and 19 , respectively ( Schemes 4–7 ). In the reaction of 14 with 6 , the 1,3‐oxathiolane 20 with a Ph group at C(2) was also formed. The structures of 3, 7, 8, 10, 19 , and 20 were established by X‐ray crystallography ( Figs. 1–4 ). In contrast to the thiolactones 1, 9 , and 14 , the thioesters 21a – 21d did not react with ( R )‐2‐phenyloxirane ( 6 ) either in the presence of SiO 2 or under more‐drastic conditions with BF 3 ⋅Et 2 O or SnCl 4 ( Scheme 8 ). The results show that spirocyclic 1,3‐oxathiolanes can be prepared from thiolactones with oxiranes. The nucleophilic attack of the thiocarbonyl S‐atom at the SiO 2 ‐activated oxirane ring proceeds with high regio‐ and stereoselectivity via an S N 2‐type mechanism.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

Full frame distilled prediction

Teacher imitation

Not 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.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.017
Threshold uncertainty score0.579

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.000
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

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.

Opus teacher head0.009
GPT teacher head0.215
Teacher spread0.206 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it