Synthesis of Cyclo-1,3-dien-5-ynes

Hopf, Henning; Krüger, Anke

doi:10.1002/1521-3765(20011015)7:20<4378::aid-chem4378>3.0.co;2-i

Cited by 39 publications

(33 citation statements)

References 52 publications

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“…As reported elsewhere, two of the authors successfully synthesized a series of cyclo-1,3-dien-5-ynes 11 d ± h. [68] These compounds can be obtained in overall yields between 2 and 22 % by following a synthetic route with five steps (Scheme 11); they are colorless, volatile liquids, which are stable when stored under argon and cooled.…”

Section: Resultsmentioning

confidence: 91%

The Cyclization of Parent and Cyclic Hexa-1,3-dien-5-ynes—A Combined Theoretical and Experimental Study

et al. 2001

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The thermal cycloisomerization of both parent and benzannelated hexa-1,3-dien-5-yne, as well as of carbocyclic 1,3-dien-5-ynes (ring size 7-14), was investigated by using pure density functional theory (DFT) of Becke, Lee, Yang, and Parr (BLYP) in connection with the 6-31G* basis set and the Brueckner doubles coupled-cluster approach [BCCD(T)] with the cc-pVDZ basis set for the parent system. The initial cyclization product is the allenic cyclohexa-1,2,4-triene (isobenzene), while the respective biradical is the transition structure for the enantiomerization of the two allenes. Two consecutive [1,2]-H shifts further transform isobenzene to benzene. For the benzannelated system, the energetics are quite similar and the reaction path is the same with one exception: the intermediate biradical is not a transition state but a minimum which is energetically below isonaphthalene. The cyclization of the carbocyclic 1,3-dien-5-ynes, which follows the same reaction path as the parent system, clearly depends on the ring size. Like the cyclic enediynes, the dienynes were found to cyclize to products with reduced ring strain. This is not possible for the 7- and 8-membered dienynes, as their cyclization products are also highly strained. For 9- to 11-membered carbocycles, all intermediates, transition states, and products lie energetically below the parent system; this indicates a reduced cyclization temperature. All other rings (12- to 14-membered) have higher barriers. Exploratory kinetic experiments on the recently prepared 10- to 14-membered 1,3-dien-5-ynes rings show this tendency, and 10- and 11-membered rings indeed cyclize at lower temperatures.

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Section: Resultsmentioning

confidence: 91%

The Cyclization of Parent and Cyclic Hexa-1,3-dien-5-ynes—A Combined Theoretical and Experimental Study

et al. 2001

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“…To a stirring solution of hept-6-ynal15 ( 11 ) (1.01 g, 9.14 mmol) in 75 mL of THF at 0 °C was added a solution of ethynylmagnesium bromide in THF (0.5M, 21.9 mL, 11.0 mmol). The reaction mixture was stirred at 0 °C for 2 h and then saturated NH 4 Cl (100 mL) was added.…”

Section: Methodsmentioning

confidence: 99%

Exploration of Braverman Reaction Chemistry. Synthesis of Tricyclic Dihydrothiophene Dioxide Derivatives from Bispropargyl Sulfones

Feldman¹,

Selfridge²

2010

HETEROCYCLES

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“…Hydrolysis of 12 and isomerization of internal alkynol 13 gave the terminal alkynol, 8‐nonyn‐1‐ol ( 14 ). It is noteworthy that the base‐catalyzed isomerization of the β‐alkynol we used followed the method reported previously for isomerization of γ‐alkynols to (ω‐1)‐alkyn‐1‐ols . The sequence in Scheme employing propargyl alcohol can be used for synthesis of a wide range of (ω‐1)‐alkyn‐1‐ols.…”

Section: Resultsmentioning

confidence: 99%

(ω‐2,ω‐2,ω‐3,ω‐3)‐Tetradeuterio‐fatty acids for mechanistic studies of enzyme‐catalyzed hydroxylation reactions

Horner

Newcomb

2012

Labelled Comp Radiopharmac

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Among the thousands of cytochrome P450 enzymes known, many selectively hydroxylate the hydrocarbon tail of fatty acids at the terminal (ω) position and the ω‐1, ω‐2, and ω‐3 positions. A general method for synthesis of (ω‐2,ω‐2,ω‐3,ω‐3)‐tetradeuterio‐fatty acids that can be used in mechanistic studies of cytochromes P450 is illustrated by the synthesis of 9,9,10,10‐tetradueteriododecanoic (lauric) acid and 13,13,14,14‐tetradeuteriohexadecanoic (palmitic) acid. Deuterium is introduced early in the synthesis by reduction of the THP ether of 4‐heptyn‐1‐ol with deuterium gas to give a common labeled intermediate, 4,4,5,5‐tetradeuterioheptan‐1‐ol. This alcohol is converted to the corresponding tosylate that is used to alkylate O‐protected (ω‐1)‐alkyn‐1‐ols to give, eventually, long‐chain alcohols that are oxidized to the corresponding fatty acids. An important experimental detail is that relatively large amounts of Wilkinson's catalyst were used to limit isotopic scrambling. Copyright © 2012 John Wiley & Sons, Ltd.

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Synthesis of Cyclo-1,3-dien-5-ynes

Cited by 39 publications

References 52 publications

The Cyclization of Parent and Cyclic Hexa-1,3-dien-5-ynes—A Combined Theoretical and Experimental Study

The Cyclization of Parent and Cyclic Hexa-1,3-dien-5-ynes—A Combined Theoretical and Experimental Study

Exploration of Braverman Reaction Chemistry. Synthesis of Tricyclic Dihydrothiophene Dioxide Derivatives from Bispropargyl Sulfones

(ω‐2,ω‐2,ω‐3,ω‐3)‐Tetradeuterio‐fatty acids for mechanistic studies of enzyme‐catalyzed hydroxylation reactions

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