Stereochemistry of deuteron attack of a strained bond in exo-tricyclo[3.2.1.02,4]octane

LaLonde, Robert T.; Ding, Jan-Yih; Tobias, M. A.

doi:10.1021/ja01001a044

Cited by 14 publications

(11 citation statements)

References 2 publications

(3 reference statements)

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“…Fractions 10 and 11 contained 78 mg of a liquid. The nmr spectrum was consistent with the dimethyl ether of 2-methyl-l-phenyl-1,3-butanediol: nmr (CDC13) 2.67 (s, 5), 5.6 (d, 1, 7 = 4.3 Hz), 6.68 (s, 3), 6.75 (s, 3), 6.62-6.9 (m, 1), 8.0-8.6 (m, 1), 8.93 (d, 3), 9.22 (d, 3); mass spectrum m/e (reí intensity) 208 (0.75), 176 (3.5), 161 (3), 122 (10), 121 (100), 105 (7), 91 (9), 77 (13). Reexamining the original spectra of the crude product showed that about 25 % of the total reaction was the dimethyl ether (eq 10) and the remainder was the anticipated organomercuric bromide.…”

Section: Methodssupporting

confidence: 58%

“…Fractions 7-9 contained 1.43 g of a solid that exhibited nmr bands consistent with structure 17. Several diastereomers were present, but one clearly predominated: nmr (CDC13) r 2.70 (s, 5), 6. 04 (d, 1,7= 7.5 Hz), 6.85 (s, 3), 7.3-8.2 (m, 2), 8.58 (d, 3), 9.23 (d, 3).…”

Section: Methodsmentioning

confidence: 99%

“…The two diastereomers were separated by fractional recrystallization from hexane. The major diastereomer separated out first: nmr (CDC13) 6.63 (s, 3), 6.89 (quin, 1), 7.5-8.4 (m, 2), 8.51 (d, 3), 8.79 (d, 3), 9.08 (d, 3). The mother liquor contained mostly the minor diastereomer: nmr (CDCl,) r 6.64 (s, 3), 7.22 (quartet of doublets, 1), 7.6-8.4 (m, 2), 8.59 (d, 3), 8.88 (t, 6).…”

Section: Methodsmentioning

confidence: 99%

“…The methyl ether was purified by preparative glpc: nmr (CC14) r 6.77 (s, 3), 6.9 (m, 1), 8.29-9.0 (m), 8.97 (d), 9.01 (d), 9.17 (d), 9.18 (d); ir (CC14) 2820 (m, OCH3), 1460 (s), 1380 (s), 1095 (s) cm-1. The major diastereomer should have the erythro configuration, but the complexity of the nmr spectrum made distinction of the two isomers difficult.…”

Section: Methodsmentioning

confidence: 99%

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Stereochemistry of the reaction of cyclopropanes with mercuric trifluoroacetate

DePuy¹,

McGirk²

1974

J. Am. Chem. Soc.

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The various stereoisomers of 1,2,3-trimethyl-1 -phenylcyclopropane, 2,3-dimethyl-l-phenylcyclopropane, and 2,3-dimethylcyclopropanol methyl ether have been reacted with mercuric trifluoroacetate in methanol and the stereochemistry of both electrophilic and nucleophilic attack has been determined. The electrophilic mercury reacts at the least substituted ring bond (for bonds of equal substitution attack at a cis-substituted bond is preferred over attack at a trans-substituted one). Ring opening occurs in the direction of the more stable carbonium ion, which can lead to either retention or inversion at the site of electrophilic substitution. The opening occurs with substantially complete inversion of configuration at the site of nucleophilic attack. If all ring bonds are identically substituted, as is c«-l,2,3-trimethylcyclopropane, the ring-opened product arises from 62% inversion and 38% retention of configuration at the site of mercury attack and 100% inversion by the methanol. The results seem best to be accounted for by the formation, in the rate-determining step, of a corner-mercurated cyclopropane which ring opens by nucleophilic substitution by solvent.

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Section: Methodssupporting

confidence: 58%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Stereochemistry of the reaction of cyclopropanes with mercuric trifluoroacetate

DePuy¹,

McGirk²

1974

J. Am. Chem. Soc.

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“…(9). The case studied was the exo isomer of tricyclo [3.2.1.02,4]octane (14) which opens the internal cyclopropane bond with inversion by the attacking D+; the deuteron becomes attached to the rear of tile carbon when the C-C bond is broken.…”

Section: A Stereochemistry Of the Attack Of The Protonmentioning

confidence: 99%

Stereochemistry and reactivity in cyclopropane ring-cleavage by electrophiles

DePuy

Three-Membered Rings

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Cyclopropanes from Unsaturated Compounds, Methylene Iodide, and Zinc‐Copper Couple

et al. 2011

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The reaction of the organozinc reagent prepared from methylene iodide and zinc‐copper couple with substituted unsaturated compounds has proved to be a versatile and convenient method for the synthesis of cyclopropanes. The synthesis is stereospecific with regard to the stereochemistry of the unsaturated compound and is usually free from serious side reactions; it can be carried out under mild conditions in diethyl and affords cyclopropanes often in good yields. This method can be easily adapted to large‐scale preparations. Two useful variations of the cyclopropanation reaction have appeared which involve the same or a similar organozinc intermediate: (1) diazomethane reacts with iodide in ether to form a reagent which converts unsaturated compounds to cyclopropanes; (2) methlyene iodide and diethyl zinc react in ether in the presence of unsaturated compounds to cyclopropanes. Processes are known in which a divalent carbon fragment adds to carbon‐carbon double bonds either as a free carbene or as an organometallic complex.

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Stereochemistry of deuteron attack of a strained bond in exo-tricyclo[3.2.1.02,4]octane

Cited by 14 publications

References 2 publications

Stereochemistry of the reaction of cyclopropanes with mercuric trifluoroacetate

Stereochemistry of the reaction of cyclopropanes with mercuric trifluoroacetate

Stereochemistry and reactivity in cyclopropane ring-cleavage by electrophiles

Cyclopropanes from Unsaturated Compounds, Methylene Iodide, and Zinc‐Copper Couple

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