Stereochemistry of the lithium aluminum deuteride reduction of the thiirane ring

Helmkamp, George K.; Schnautz, N. G.

doi:10.1016/0040-4020(58)88051-5

Cited by 22 publications

(9 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This plot covers 42 of the 50 molecules of our test set. Only the helicene derivatives (31)(32)(33)(34)(35), norbornenone (15), the steroid (30), and cyclooctene (49) have been excluded because of their high optical rotations.…”

Section: Resultsmentioning

confidence: 99%

Optical rotation calculations on large molecules using the approximate coupled cluster model CC2 and the resolution-of-the-identity approximation

Friese

Hättig

2014

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

We investigate the performance of the approximate coupled cluster singles- and doubles model CC2 in the prediction of optical rotations of organic molecules. For this purpose we employ a combination of two test sets from the literature which include small and medium-sized rigid organic molecules and a series of helicenes. CC2 calculations on molecules as large as 11-helicene became possible through a recent implementation of frequency-dependent second-order properties for CC2 which makes use of the resolution-of-the-identity approximation for the electron repulsion integrals. The results are assessed with respect to the accuracy of the absolute values of the optical rotation and the prediction of the correct sign, which is crucial for the determination of absolute configurations. The performance of CC2 is compared with that of density functional theory at the B3LYP and CAM-B3LYP levels. Furthermore we investigated the influence of the molecular geometry and the one-electron basis set and tested to which extent spin-component scaling changes the results.

show abstract

Section: Resultsmentioning

confidence: 99%

Optical rotation calculations on large molecules using the approximate coupled cluster model CC2 and the resolution-of-the-identity approximation

Friese

Hättig

2014

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…By-products of the reduction are solid polymers and sulfurcontaining liquids, but not hydrogen sulfide (153). By the use of lithium aluminum deuteride it was demonstrated that the reduction of 2-butene sulfide involves inversion of the configuration (96).…”

Section: Reductionmentioning

confidence: 99%

“…Acetic acid causes slow polymerization of ethylene sulfide, while propene sulfide and 1-butene sulfide show no change (50, 51). On boiling with excess glacial acetic acid, cyclohexene sulfide forms 26% monomeric and 48% dimeric acetoxy mercaptan (96). Treatment of thiiranes with excess iodine in glacial acetic acid results in quantitative formation of the acetoxy disulfide so that this reaction can be used for iodometric determination of thiiranes (192).…”

Section: K Reaction With Carboxylic Acidsmentioning

confidence: 99%

“…By interaction of the corresponding alkene oxides with thiourea the following thiiranes have been prepared: ethylene sulfide (42,76,91), propene sulfide (18,21,37,43,46,92), chloropropene sulfide (37,44,46,75), 2-butene sulfide (96), isobutene sulfide (37), butadiene monosulfide (38), 1-hexene sulfide (22), 1-octene sulfide (153), cyclohexene sulfide (37), 4-methylcyclohexene sulfide (38) stilbene sulfides (115), thioglycidyl ethers (5, 205), thioglycidyl sulfides and thioglycidyl amines (5, 204), various bis (thioglycidyl) ethers (135), thiirane fatty acids, fatty esters, and fatty alcohols (60,113,172). Thiiranes could not be prepared from the following alkene oxides by means of thiourea: glycidol (5,37), styrene oxide (37), ethyl dimethylglycidate (37), ethyl phenylglycidate (39), other glycidates (29,60), glycidamides (243), benzylideneacetone oxide (37), stilbene oxide (37), cyclopentene oxide (21).…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Thiiranes

Sander¹

1966

Chem. Rev.

260

101

View full text Add to dashboard Cite

“…We have shown that the nucleophile-induced opening of thietane rings occurs by back-side addition to the carbon atoms bonded to the sulfur atom . There is evidence that the ring opening of thiiranes by nucleophiles also occurs by back-side addition to one of the carbon atoms …”

Section: Discussionmentioning

confidence: 94%

Catalytic Transformations of Thiiranes by (Thiirane)W(CO)₅Complexes

Adams¹,

Yamamoto²,

Holmes³

et al. 1997

Organometallics

View full text Add to dashboard Cite

The thiirane complexes W(CO)5(SCH2CH2), 1, W(CO)5(cis-SCHMeCHMe), 2, and W(CO)5(trans-SCHMeCHMe), 3, have been prepared and characterized. The molecular structure of compound 2 was also determined crystallographically. It was found to contain an S-coordinated cis-dimethylthiirane ligand with a pyramidal sulfur atom coordinated to a W(CO)5 group. Compounds 1−3 decompose slowly to yield sulfur and the corresponding olefin. Compound 1 and W(CO)5(NCMe) were both found to transform free thiirane into a mixture of cyclic polydisulfides (SCH2CH2S) n , 4−7, n = 2, 3, 4, and 5, and ethylene, catalytically. The turnover frequency for the formation of 4 by 1 at 25°C is 6.8 h-1. When the catalytic reaction was performed in the presence of dimethylacetylenedicarboxylate, DMAD, compounds 4 and 5 and the six-membered heterocycle SCH2CH2SC(CO2Me)C(CO2Me), 8 were formed, the last by the trapping of a suspected SCH2CH2S intermediate. Small amounts of polythioether macrocycles (CH2CH2S) n , 12S4, n = 4, and 15S5, n = 5, were also formed. (2R,3S)-dimethylthiirane (cis-DMT) and (2R,3R(2S,3S))-dimethylthiirane (trans-DMT) undergo a combination of isomerization and desulfurization to yield a mixture of cis- and trans-butene by 2 and 3, respectively. In the presence of DMAD, the isomerization of the substituted thiiranes is suppressed and small amounts of the cyclic disulfides [C(H)CH3C(H)CH3SS]3, 9, and [C(H)CH3C(H)SS]2, 10, and the cyclic trisulfide (4S,5S(4R,5R))-[S3C(H)CH3C(H)CH3], 12, were formed. The molecular structure of 9 was determined crystallographically and established a pattern of identical R,R/S,S stereochemistries at adjacent stereogenic carbon atoms about the ring. A similar stereochemical result was indicated for the stereogenic carbon centers in 12 by preparing the osmium complex Os2(CO)6[μ-(R,R(S,S))-SC(H)CH3C(H)CH3S], 13, from it and determining the configurations at the stereogenic carbon atoms in the SC(H)CH3C(H)CH3S ligand by an X-ray crystallographic analysis. All of the catalytic transformations can be explained by a back-side addition of a sulfur atom from an uncoordinated molecule of thiirane to a carbon atom of a thiirane ligand. This leads to an opening of the thiirane ligand and formation of a zwitterionic thiiranium/thiolato intermediate having the thiolato sulfur atom coordinated to the tungsten atom. Release of the added thiirane from a conformer for the zwitterion would result in isomerization of the thiirane ligand. Alternatively, loss of olefin from the thietanium ion group would yield a (SCH2CH2S)W(CO)5 intermediate that could decompose by loss of SCH2CH2S groups, which could then combine to form the cyclic disulfides, 4−7. In the presence of DMAD, the SCH2CH2S group is trapped to yield 8. A series of similar ring-opening additions followed by a cyclization could lead to the formation of the polythioether macrocycles 12S4 and 15S5, but these compounds are minor products even under the best conditions. It was also found that compound 4 has moderate antimicrobial activity toward Escherichia coli.

show abstract

Stereochemistry of the lithium aluminum deuteride reduction of the thiirane ring

Cited by 22 publications

References 19 publications

Optical rotation calculations on large molecules using the approximate coupled cluster model CC2 and the resolution-of-the-identity approximation

Optical rotation calculations on large molecules using the approximate coupled cluster model CC2 and the resolution-of-the-identity approximation

Thiiranes

Catalytic Transformations of Thiiranes by (Thiirane)W(CO)₅Complexes

Contact Info

Product

Resources

About

Stereochemistry of the lithium aluminum deuteride reduction of the thiirane ring

Cited by 22 publications

References 19 publications

Optical rotation calculations on large molecules using the approximate coupled cluster model CC2 and the resolution-of-the-identity approximation

Optical rotation calculations on large molecules using the approximate coupled cluster model CC2 and the resolution-of-the-identity approximation

Thiiranes

Catalytic Transformations of Thiiranes by (Thiirane)W(CO)5Complexes

Contact Info

Product

Resources

About

Catalytic Transformations of Thiiranes by (Thiirane)W(CO)₅Complexes