Monoozonides of chloro-substituted conjugated dienes: preparation, stability, and some chemical reactions

Griesbaum, Karl; Bandyopadhyay, Ashis R.; Meister, Martin

doi:10.1139/v86-256

Cited by 14 publications

(6 citation statements)

References 9 publications

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“…Several unsaturated bicyclic unsaturated ozonides were reduced by diimide to give saturated ozonides . Ozonolysis of a vinyl chloride ozonide in methanol afforded the corresponding methyl ester ozonide . Successive treatment of another vinyl chloride ozonide with m -CPBA and AgBF 4 afforded an enone ozonide via an epoxy ozonide …”

mentioning

confidence: 99%

Synthesis of Tetrasubstituted Ozonides by the Griesbaum Coozonolysis Reaction: Diastereoselectivity and Functional Group Transformations by Post-Ozonolysis Reactions

et al. 2004

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The diastereoselectivity of the Griesbaum coozonolysis reaction with O-methyl 2-adamantanone oxime and 4-substituted cyclohexanones reveals that the major tetrasubstituted ozonide isomers possess cis configurations, suggesting a preferred axial attack of the carbonyl oxide on the cyclohexanone dipolarophiles. It is evident that these tetrasubstituted ozonides are quite stable to triphenylphosphine, borohydrides, hydrazine, alkyllithiums, Grignard reagents, mercaptides, and aqueous KOH as illustrated by the synthesis of amine, alcohol, acid, ester, ether, sulfide, sulfone, and heterocycle-functionalized ozonides by a wide range of post-ozonolysis transformations.

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confidence: 99%

Synthesis of Tetrasubstituted Ozonides by the Griesbaum Coozonolysis Reaction: Diastereoselectivity and Functional Group Transformations by Post-Ozonolysis Reactions

et al. 2004

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“…Completion of the synthesis of isovelleral could be achieved by following the reaction sequence shown in Scheme . Ozonolysis of 45 and reduction with NaBH 4 furnished, after purification, alcohol 49 in 39% yield …”

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confidence: 99%

A Novel Route to the Marasmane Skeleton via a Tandem Rearrangement−Cyclopropanation Reaction. Total Synthesis of (+)-Isovelleral

2001

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A general and efficient route to the marasmane skeleton is described. Total syntheses of two simple marasmanes (35 and 37) in racemic form were achieved using a MgI2-catalyzed rearrangement-cyclopropanation reaction of trimethylsilyl enol ether 31 derived from naphthalenone 30. The reaction proceeds in high yield with complete diastereoselectivity and does not require the use of special cyclopropanation reagents. Application of this novel route to the marasmane framework was extended to the synthesis of naturally occurring (+)-isovelleral (41).

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“…A mixture of 278 mg (1.9 mmol) of 4a (8). 217 mg (1.3 mmol) of 1,1,2,2-tetrachloroethane, and 38 1 mg (1 1.9 mmol) of methanol was ozonized to completion at -60°C, flushed with nitrogen, and divided into two parts.…”

Section: Diozonolysis Of 4amentioning

confidence: 99%

“…A solution of 314 mg (2.0 mmol) of 4b (8), 236 mg (1.4 mmol) of 1,1,2,2-tetrachloroethane, and 234 mg (7.3 mmol) of methanol in 2mL of CDC13 was treated with 763 mg (1.5 mmol) of ozone at -55"C, admixed with 27 mg (0.5 mmol) of sodium methoxide, and warmed up to room temperature. The 'H nrnr analysis showed the presence of 2, 6 , 7 (8) 3 1 mmol) of methanol in 2mL of CDC13, which had been shaken with potassium carbonate, was ozonized at -60°C and divided into two parts.…”

Section: Morzoozonolysis Of 4bmentioning

confidence: 99%

“…The 'H nrnr analysis showed the presence of 2, 6 , 7 (8) 3 1 mmol) of methanol in 2mL of CDC13, which had been shaken with potassium carbonate, was ozonized at -60°C and divided into two parts. One part was warmed up to room temperature; 'H nmr analysis of the strongly peroxidic solution showed the presence of 2 and of 12 in yields of 82 and 79%, respectively.…”

Section: Morzoozonolysis Of 4bmentioning

confidence: 99%

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Anomalous ozone degradations of 1-chloro substituted conjugated dienes in methanol

Griesbaum¹,

Bandyopadhyay²

1987

Can. J. Chem.

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KARL GRIESBAUM and ASHIS R. BANDYOPADHYAY. Can. J. Chem. 65, 487 (1987). Diozonolyses in methanol of (E~-4-chloro-2,3-dimethyl-1,3-hexadiene (40) and of (4E)-5-chloro-3,4-dimethyl-2,4-heptadiene (4b) resulted in complete cleavage of the double bonds and of the single bonds of the respective diene systems. The course of these anomalous cleavage reactions has been established by step-wise ozonolyses of these dienes, and by the identification of labile methoxy hydroperoxides as intermediates.KARL GRIESBAUM et ASHIS R. BANDYOPADHYAY. Can. J. Chem. 65, 487 (1987). La diozonolyse du chloro-4 dimkthyl-2,3 hexadiene-1,3-(E) (4a) et du chloro-5 dimkthyl-3,4 heptadiene-2,4-(E4) (4b), dans le mkthanol, conduit 21 une coupure complete des doubles et des simples liaisons des systemes dikniques respectifs. On a determink le cours de ces rkactions de coupures anormales en prockdant a l'ozonolyse par etape de ces diknes ainsi qu'a l'identification des mkthoxy hydroperoxydes labiles comme intermkdiaires.[Traduit par la revue] Introduction product 2 was lowered from 96% after direct warm-up to 60% previous work we obtained the chlorinated diene 1 as one after DMS-d6 treatment in the ozonolysis of 4a and from 95 to of several products from the reaction of anhydrous hydrogen 18% in the OzOnO1~sis 4b. chloride with 2-butyne (1).an attempt to confirm this These results demonstrated that 4a and 4 b underwent anomstructure by ozone degradation, we observed an anomalous alous ozonolysis reactions, similar to that observed for 1, viz. ozonolysis of 1 in methanol, which resulted in the cleavage of by cleavage of the double bonds and the sing1e the double bonds and of the single bond of the diene system to of the respective conjugated diem systems. The fact that the give fragments 2 and 3 in a ratio of 3: 1 (2). extent of the abnormal cleavage could be lowered by reduction of the product mixture indicated, however, that it did not occur CH3 CH3 CH3 C1

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Monoozonides of chloro-substituted conjugated dienes: preparation, stability, and some chemical reactions

Cited by 14 publications

References 9 publications

Synthesis of Tetrasubstituted Ozonides by the Griesbaum Coozonolysis Reaction: Diastereoselectivity and Functional Group Transformations by Post-Ozonolysis Reactions

Synthesis of Tetrasubstituted Ozonides by the Griesbaum Coozonolysis Reaction: Diastereoselectivity and Functional Group Transformations by Post-Ozonolysis Reactions

A Novel Route to the Marasmane Skeleton via a Tandem Rearrangement−Cyclopropanation Reaction. Total Synthesis of (+)-Isovelleral

Anomalous ozone degradations of 1-chloro substituted conjugated dienes in methanol

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