Regioselective Synthesis of Medium-Sized Bicyclic Butenolides by Lewis Acid Catalyzed Cyclization of Cyclic 1,3-Bis(trimethylsilyloxy)-1,3-butadienes with Oxalyl Chloride

Langer, Peter; Saleh, N. S.

doi:10.1021/ol006419b

Cited by 17 publications

(8 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Starting with cyclic bis(silyl enol) ethers, a number of biologically relevant bicyclic g-alkylidenebutenolides were prepared in good yields. [16] For example, the 5,10-bicyclic core structure of 3 f is present in a number of sesquiterpenes.…”

Section: Discussionmentioning

confidence: 99%

“…[12,16] Due to their polyketide structure, many natural products contain an oxygen atom at carbon C(4) of the butenolide moiety. The preparation of g-alkylidenetetronic acids and esters from ascorbic acid derivatives requires several steps and has the disadvantage that no additional substituents can be introduced at the exocyclic double bond or at the butenolide moiety.…”

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Regio- and Diastereoselective Cyclization Reactions of Free and Masked 1,3-Dicarbonyl Dianions with 1,2-Dielectrophiles

Langer¹

2001

Chem. Eur. J.

Self Cite

View full text Add to dashboard Cite

Despite their simplicity and synthetic usefulness, cyclisation reactions of 1,3-dicarbonyl dianions with 1,2-dielectrophiles are problematic, since both dianions and 1,2-dielectrophiles are highly reactive compounds (low reactivity matching). In addition, 1,2-dielectrophiles are often rather labile, and reactions with nucleophiles can result in polymerisation, decomposition, formation of open-chained products, elimination or SET-reactions. These intrinsic limitations can be overcome by a proper reactivity tuning and by the use of electroneutral dianion equivalents (masked dianions) in Lewis acid catalysed reactions. The cyclisations reported herein allow for an efficient, regio- and stereoselective one-pot synthesis of biologically relevant ring systems.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Regio- and Diastereoselective Cyclization Reactions of Free and Masked 1,3-Dicarbonyl Dianions with 1,2-Dielectrophiles

Langer¹

2001

Chem. Eur. J.

Self Cite

View full text Add to dashboard Cite

show abstract

“…For the synthesis of -alkylidenebutenolides, see: Park et al (2012); Almeida et al (2010); Xu et al (2007); Langer et al ( , 2001. For related structures, see: Schneider & Viljoen (1997); Langer & Saleh (2000). For standard bond lengths, see: Allen et al (1987) and for puckering parameters, see: Cremer & Pople (1975).…”

Section: Related Literaturementioning

confidence: 99%

“…As a result, several synthetic procedures have been developed for the preparation of these substances Langer, et al, 2001;Xu, et al, 2007;Almeida, et al, 2010;Park, et al, 2012). Also, α-Hydroxy-γ-alkylidenebutenolides are particularly suitable building blocks for analogues of pharmacologically relevant natural products (Langer & Saleh, 2000). Herein, we report the crystal structure of a bicyclic α-hydroxy-γ-alkylidenebutenolide based on l-Menthone, an inexpensive and accessible reagent from the chiral pool, which is also an important structural motif found in natural products.…”

Section: S1 Introductionmentioning

confidence: 99%

(4R)-3-Hydroxy-7-isopropyl-4-methyl-5,6-dihydrobenzofuran-2(4H)-one

et al. 2014

View full text Add to dashboard Cite

In the title compound, alternatively called α-hydroxy-γ-alkylidenebutenolide, C12H16O3, two independent molecules (A and B) crystallize in the asymmetric unit in each of which the 5,6-dihydrobenzo ring has an envelope conformation. The torsion angle along the butadiene chain in the γ-alkylidenebutenolide core is −177.9 (2)° for molecule A and 179.9 (2)° for molecule B. In the crystal, O—H⋯O hydrogen bonds between hydroxyl and carbonyl groups of adjacent independent molecules form dimers with R 2 2(10) loops.

show abstract

“…20,21 Bicyclic butenolides occur in a number of sesquiterpene natural products, such as the germacranolides. …”

Section: Scope and Limitationsmentioning

confidence: 99%

Synthesis of Butenolides by One-Pot Cyclization Reactions of Silyl Enol Ethers with Oxalyl Chloride

Langer¹

2006

Synlett

Self Cite

View full text Add to dashboard Cite

Oxalyl chloride represents a versatile C 2 building block for cyclization reactions. A variety of cyclization reactions of oxalyl chloride are known which involve the formation of two carbon-heteroatom bonds. In contrast, one-pot cyclizations of oxalyl derivatives which proceed by formation of at least one carbon-carbon bond are more rare. In recent years, a number of such cyclizations have been developed which rely on the reaction of oxalyl chloride with silyl enol ethers. These reactions allow for an efficient synthesis of various oxygen heterocycles, such as g-alkylidenebutenolides, maleic anhydrides and isotetronic acids. The cyclization reactions, which involve the formation of a carbon-carbon and a carbon-oxygen bond, generally proceed with excellent regioselectivity.

show abstract

Regioselective Synthesis of Medium-Sized Bicyclic Butenolides by Lewis Acid Catalyzed Cyclization of Cyclic 1,3-Bis(trimethylsilyloxy)-1,3-butadienes with Oxalyl Chloride

Abstract: A new strategy for the synthesis of medium-sized bicyclic gamma-alkylidenebutenolides is reported which involves Me(3)SiOTf-catalyzed cyclization of cyclic 1, 3-bis(trimethylsilyloxy)-1,3-butadienes with oxalyl chloride.

Cited by 17 publications

References 26 publications

Regio- and Diastereoselective Cyclization Reactions of Free and Masked 1,3-Dicarbonyl Dianions with 1,2-Dielectrophiles

Regio- and Diastereoselective Cyclization Reactions of Free and Masked 1,3-Dicarbonyl Dianions with 1,2-Dielectrophiles

(4R)-3-Hydroxy-7-isopropyl-4-methyl-5,6-dihydrobenzofuran-2(4H)-one

Synthesis of Butenolides by One-Pot Cyclization Reactions of Silyl Enol Ethers with Oxalyl Chloride

Contact Info

Product

Resources

About