Intramolecular Haloetherification and Transannular Hydroxycyclization of Alkenes. A Synthetic Methodology to Obtain Polycyclic Ethers and Amines

Montaña, Ángel M.; Batalla, Consuelo; Barcia, Juan A.

doi:10.2174/138527209788452135

Cited by 32 publications

(7 citation statements)

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“…Bromocycloetherification of olefins [1][2][3][4] is an interesting and useful synthetic transformation, with proven application to the synthesis of biologically relevant molecules. [5][6][7][8][9][10][11][12][13] The bromo ether products can be valuable synthetic intermediates, 11 or natural product targets themselves. 9,10,12,13 Surprisingly, methods for the enantioselective synthesis of bromo ethers have only recently been reported.…”

Section: Introductionmentioning

confidence: 99%

Development and Mechanism of an Enantioselective Bromocycloetherification Reaction via Lewis Base/Chiral Brønsted Acid Cooperative Catalysis

Denmark

Burk

2013

Chirality

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Section: Introductionmentioning

confidence: 99%

Development and Mechanism of an Enantioselective Bromocycloetherification Reaction via Lewis Base/Chiral Brønsted Acid Cooperative Catalysis

Denmark

Burk

2013

Chirality

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“…1), are versatile synthetic transformations with proven applications to the synthesis of biologically relevant molecules (1)(2)(3)(4)(5)(6). The development of catalytic enantioselective halocyclization methods is a topic of increasing interest in synthetic organic chemistry, one that presents unique challenges and opportunities for various paradigms of catalysis in addition to the obvious importance and utility of this transformation.…”

mentioning

confidence: 99%

Lewis base catalysis of bromo- and iodolactonization, and cycloetherification

Denmark

Burk

2010

Proc. Natl. Acad. Sci. U.S.A.

234

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Lewis base catalyzed bromo-and iodolactonization reactions have been developed and the effects of catalyst structure on rate and cyclization selectivity have been systematically explored. The effects of substrate structure on halolactonization reactions and the interaction of those effects with the effects of catalyst structure have been investigated, leading to synthetically useful improvements in cyclization selectivity. The knowledge acquired was applied to the development of Lewis base catalyzed bromoand iodocycloetherification reactions. The ability of some of the surveyed catalysts to influence the cyclization selectivity of halolactonization reactions demonstrates their presence in the transition structure of the product-determining cyclization step. This observation implies that chiral derivatives of these catalysts have the potential to provide enantioenriched products regardless of the rates or mechanisms of halonium ion racemization.halocyclofunctionalization | halogenation E lectrophilic halocyclizations of olefins, in which electrophilic halonium ions are generated from olefins and opened intramolecularly by nucleophilic functional groups (Fig. 1), are versatile synthetic transformations with proven applications to the synthesis of biologically relevant molecules (1-6). The development of catalytic enantioselective halocyclization methods is a topic of increasing interest in synthetic organic chemistry, one that presents unique challenges and opportunities for various paradigms of catalysis in addition to the obvious importance and utility of this transformation. To date, only a few notable successes have been reported; these include the use of chiral Ti-salen complexes in iodoetherification (7) and cinchonidinium phasetransfer catalysts in iodolactonization (8). Recently, modified Cinchona alkaloids have been successfully employed in catalytic enantioselective chlorolactonization (9), as well as a catalytic enantioselective bromolactonization of 1,3-eneynes via conjugate opening of achiral bromonium ions (10-15*).Careful mechanistic studies by Brown and coworkers and from these laboratories identified a serious obstacle to the development of catalytic enantioselective iodination and bromination methods, namely the propensity of iodonium and bromonium ions (but not chloronium ions) to undergo degenerate halogen exchange with olefins ( Fig. 2) (16-19). This process racemizes the halonium ions at rates that can compete with nucleophilic capture. Chiral Lewis base catalysts have the potential to prevent this or other racemization processes, if they remain bound to the halonium ion until the newly created stereocenters are irreversibly set, thus maintaining a chiral environment regardless of exchange. Lewis base catalysis of halogenation has been reported in several different contexts (20-23), as have enantioselective halocyclization reactions promoted by stoichiometric amounts of chiral Lewis bases (13-15), but the paucity of catalytic, enantioselective Lewis base catalyzed halogenations suggests that ...

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“…The halocyclization of alkenes provides an excellent synthetic method for halogenated heterocycles [ 1 – 3 ]. In recent years, haloaminocyclization [ 4 – 5 ], halolactonization [ 6 – 7 ] and haloetherification [ 8 – 9 ] of alkenes have received considerable attention from chemists, and various approaches have been made in this area. Initially, the classical synthetic pathway for bromocyclization proceeds utilizing bromine [ 10 ].…”

Section: Introductionmentioning

confidence: 99%

Visible-light-induced bromoetherification of alkenols for the synthesis of β-bromotetrahydrofurans and -tetrahydropyrans

Lin¹,

Sun²,

Yang³

et al. 2015

Beilstein J. Org. Chem.

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Intramolecular Haloetherification and Transannular Hydroxycyclization of Alkenes. A Synthetic Methodology to Obtain Polycyclic Ethers and Amines

Cited by 32 publications

References 0 publications

Development and Mechanism of an Enantioselective Bromocycloetherification Reaction via Lewis Base/Chiral Brønsted Acid Cooperative Catalysis

Development and Mechanism of an Enantioselective Bromocycloetherification Reaction via Lewis Base/Chiral Brønsted Acid Cooperative Catalysis

Lewis base catalysis of bromo- and iodolactonization, and cycloetherification

Visible-light-induced bromoetherification of alkenols for the synthesis of β-bromotetrahydrofurans and -tetrahydropyrans

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