Intramolecular [6 + 4] cycloaddition: intramolecular control of periselectivity

Gupta, Y. N.; Doa, Maria J.; Houk, K. N.

doi:10.1021/ja00389a083

Cited by 39 publications

(7 citation statements)

References 2 publications

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“…Hence, EDG stabilise pentafulvenes ( 3b’ ), whereas EWG stabilise heptafulvenes ( 6b’ ) [9,67]. In many cases, the reactions of fulvenes are peri- [17,22,28,73–80], enantio- [81–87], diastereo- [17,21,26,28,81,88–92], and regioselective [17,28,74–76 81–82 93–94], and result from the electronic nature of the fulvene, the reactant partner, as well as steric arguments.…”

Section: Reviewmentioning

confidence: 99%

An overview of the cycloaddition chemistry of fulvenes and emerging applications

Swan¹,

Platts²,

Blencowe³

2019

Beilstein J. Org. Chem.

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The unusual electronic properties and unique reactivity of fulvenes have interested researchers for over a century. The propensity to form dipolar structures at relatively low temperatures and to participate as various components in cycloaddition reactions, often highly selectively, makes them ideal for the synthesis of complex polycyclic carbon scaffolds. As a result, fulvene cycloaddition chemistry has been employed extensively for the synthesis of natural products. More recently, fulvene cycloaddition chemistry has also found application to other areas including materials chemistry and dynamic combinatorial chemistry. This highlight article discusses the unusual properties of fulvenes and their varied cycloaddition chemistry, focussing on applications in organic and natural synthesis, dynamic combinatorial chemistry and materials chemistry, including dynamers, hydrogels and charge transfer complexes. Tables providing comprehensive directories of fulvene cycloaddition chemistry are provided, including fulvene intramolecular and intermolecular cycloadditions complete with reactant partners and their resulting cyclic adducts, which provide a useful reference source for synthetic chemists working with fulvenes and complex polycyclic scaffolds.

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Section: Reviewmentioning

confidence: 99%

An overview of the cycloaddition chemistry of fulvenes and emerging applications

Swan¹,

Platts²,

Blencowe³

2019

Beilstein J. Org. Chem.

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“…hirsutene, capnellene, vetivone, viburtinal, hinesol, silphinene and longifolene. 2 The use of fulvenes as 6p components in many inter- 3 and intramolecular 4 [6+4] cycloadditions is well known. Many intermolecular 5 and intramolecular 6 [4+2] cycloaddition reactions involving fulvenes as 4p or 2p 7 components have also been reported in the literature.…”

mentioning

confidence: 99%

Novel Intermolecular [3 + 2] Cycloaddition Reaction of Carbonyl Ylides with Fulvenes: Entry into the Oxatetracyclo[6.5.1.01,6.09,13]tetradecene Ring System

Muthusamy¹,

Babu²,

Gunanathan³

et al. 2001

Synlett

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Reaction of a-diazo carbonyl compounds 1/2 in the presence of rhodium(II) acetate dimer with pentafulvenes 3/6 generating the novel oxatetracyclo[6.5.1.0 1,6 .0 9,13 ]tetradecene ring systems in good yield, is reported. In the presence of unsymmetrical and symmetrical fulvenes, the products were obtained as regioisomers in the ratio of 1:2 and 1:10, respectively. The single crystal X-ray analysis of compound 4b is reported to firmly establish the stereochemistry of regioisomers.

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“…The mechanism for formation of the carbene 7 from the activated propargyl alcohol 2 is not certain. Both direct conversion of the O -acetate (or the allenyl isomer 9 ) to carbene 7 and pathways involving the stabilized carbocation 10 or the o -quinodimethide 11 have been considered. Involvement of carbocation 10 in the rate-limiting step is unlikely on the basis of no solvent effect on the reaction rate, and the observed terminal acetylene substituent effects; similarly, a noncarbene pathway involving rate limiting formation of the cyclic carbocation 12 has also been ruled out on the basis of no observed electronic effect for substituents in the trityl group.…”

mentioning

confidence: 99%

Rapid Assembly of Substituted Dihydrocyclohepta[3,4]pyrrolo[1,2-a]indoles via a Novel, Carbene-Based, Rearrangement Reaction

et al. 2000

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Intramolecular [6 + 4] cycloaddition: intramolecular control of periselectivity

Cited by 39 publications

References 2 publications

An overview of the cycloaddition chemistry of fulvenes and emerging applications

An overview of the cycloaddition chemistry of fulvenes and emerging applications

Novel Intermolecular [3 + 2] Cycloaddition Reaction of Carbonyl Ylides with Fulvenes: Entry into the Oxatetracyclo[6.5.1.01,6.09,13]tetradecene Ring System

Rapid Assembly of Substituted Dihydrocyclohepta[3,4]pyrrolo[1,2-a]indoles via a Novel, Carbene-Based, Rearrangement Reaction

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