The Use of Bicyclo[3.2.0]heptanones as Versatile Synthons in Organic Chemistry

Ali, S. Mubarik; Lee, Thomas V.; Roberts, Stanley M.

doi:10.1055/s-1977-24302

Cited by 33 publications

(7 citation statements)

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“…[22,35] Early routes Gordonetal. All routes to bicyclic derivatives exploit [2+ +2] cycloaddition reactions to construct the fourmembered cyclic ketone.…”

Section: Synthesismentioning

confidence: 99%

“…[22,35] Early routes Gordonetal. [35] Cleavageo ft he mercaptofulvene group in 17 by formic acid and two equivalents of mercuricc hloride produced both the carboxylic acid 18 and thioester 19 in a1 :4 ratio, and 16 % combinedy ield over three steps from cyclopentadiene, precursor to fulvene 16.Carboxylic acid 18 andthioester 19 were isolated as single diastereomers (Scheme 4), and their regiochemistries and relative stereochemistriesw ere confirmed by comparisono f 1 HNMR data with dataf or related compounds and X-ray crystallographic analysiso f18.F rom carboxylica cid 18, reductived echlorination using zinc and acetic acid followed by catalytic hydrogenation afforded carbapenam-cyclobutanone 12.F rom thioester 19,h ydrolysis using am ixture of concentrated hydrochlorica cid and glacial acetic acid followed by zinc/acetic acid dechlorination gave carbapenem analogue 14. 4a-Carboxybicyclo[3.2.0]heptane-6-one (12)w as conceived as as implified isostericm odel of penicillanic acid ( 13) Both 12 and 14 were synthesised in racemic form from 6,6bis-methylmercaptofulvene (16)and dichloroketene (generated in situ from dichloroacetyl chloride and an amine base) by [2+ +2] cycloaddition to form the cyclo adduct 17 (Scheme 4).…”

Section: Synthesismentioning

confidence: 99%

“…[22] ChemBioChem 2017, 18,338 -351 www.chembiochem.org Both 12 and 14 were synthesised in racemic form from 6,6bis-methylmercaptofulvene (16)and dichloroketene (generated in situ from dichloroacetyl chloride and an amine base) by [2+ +2] cycloaddition to form the cyclo adduct 17 (Scheme 4). [35] Cleavageo ft he mercaptofulvene group in 17 by formic acid and two equivalents of mercuricc hloride produced both the carboxylic acid 18 and thioester 19 in a1 :4 ratio, and 16 % combinedy ield over three steps from cyclopentadiene, precursor to fulvene 16.Carboxylic acid 18 andthioester 19 were isolated as single diastereomers (Scheme 4), and their regiochemistries and relative stereochemistriesw ere confirmed by comparisono f 1 HNMR data with dataf or related compounds and X-ray crystallographic analysiso f18.F rom carboxylica cid 18, reductived echlorination using zinc and acetic acid followed by catalytic hydrogenation afforded carbapenam-cyclobutanone 12.F rom thioester 19,h ydrolysis using am ixture of concentrated hydrochlorica cid and glacial acetic acid followed by zinc/acetic acid dechlorination gave carbapenem analogue 14.…”

Section: Early Routesmentioning

confidence: 99%

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Cyclobutanone Analogues of β‐Lactam Antibiotics: β‐Lactamase Inhibitors with Untapped Potential?

Devi

Rutledge

2017

ChemBioChem

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β-Lactam antibiotics have been used for many years to treat bacterial infections. However the effective treatment of an increasing range of microbial infections is threatened by bacterial resistance to β-lactams: the prolonged, widespread (and at times reckless) use of these drugs has spawned widespread resistance, which renders them ineffective against many bacterial strains. The cyclobutanone ring system is isosteric with β-lactam: in cyclobutanone analogues, the eponymous cyclic amide is replaced with an all-carbon ring, the amide N is substituted by a tertiary C-H α to a ketone. Cyclobutanone analogues of various β-lactam antibiotics have been investigated over the last 35 years, initially as prospective antibiotics in their own right and inhibitors of the β-lactamase enzymes that impart resistance to β-lactams. More recently they have been tested as inhibitors of other serine proteases and as mechanistic probes of β-lactam biosynthesis. Cyclobutanone analogues of the penam ring system are the first reversible inhibitors with moderate activity against all classes of β-lactamase; other compounds from this family inhibit Streptomyces R61 dd-carboxypeptidase/transpeptidase, human neutrophil elastase and porcine pancreatic elastase. But has their potential as enzyme inhibitors been fully exploited? Challenges in synthesising diversely functionalised cyclobutanone derivatives mean that only a limited number have been made (with limited structural diversity) and evaluated. This review surveys the different synthetic approaches that have been taken to these compounds, the investigations made to evaluate their biological activity and prospects for future developments in this area.

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“…[22,35] Early routes Gordonetal. All routes to bicyclic derivatives exploit [2+ +2] cycloaddition reactions to construct the fourmembered cyclic ketone.…”

Section: Synthesismentioning

confidence: 99%

Section: Synthesismentioning

confidence: 99%

Section: Early Routesmentioning

confidence: 99%

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Cyclobutanone Analogues of β‐Lactam Antibiotics: β‐Lactamase Inhibitors with Untapped Potential?

Devi

Rutledge

2017

ChemBioChem

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“…268 In the presence of sodium acetate in acetic acid, the four-five fused bicyclic compound could undergo enolization, addition/elimination, and fragmentation to form tropolone 75-4 . 269 This method was later applied to the total synthesis of various tropolones, 269–271 such as β-thujaplicin, by starting with isopropyl substituted cyclopentadiene 272 and a synthetic intermediate for colchicine ( 75-7 ) as shown in Scheme 75. 273 …”

Section: Synthesis Of Naturally Occurring Tropones and Tropolonesmentioning

confidence: 99%

Synthesis of naturally occurring tropones and tropolones

et al. 2014

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Tropones and tropolones are an important class of seven-membered non-benzenoid aromatic compounds. They can be prepared directly by oxidation of seven-membered rings. They can also be derived from cyclization or cycloaddition of appropriate precursors followed by elimination or rearrangement. This review discusses the types of naturally occurring tropones and tropolones and outlines important methods developed for the synthesis of tropone and tropolone natural products.

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“…In particular, the ring opening of certain fused-ring cyclobutanones, which are easily prepared by the well-established [2 + 2] cycloadditions of ketenes with various cycloalkenes, has been extensively investigated [3–8 12–14]. To achieve the ring opening, many reaction conditions have been investigated, such as acidic conditions, basic conditions, nucleophilic attack, thermolysis, and oxidizing as well as reducing conditions [4,11]. Cohen and Matz described the [1,2]- and [1,3]-acyl migration of 2-vinylcyclobutanones, leading to cyclopentenones or cyclohexenones, respectively [15].…”

Section: Introductionmentioning

confidence: 99%

Alkoxide-induced ring opening of bicyclic 2-vinylcyclobutanones: A convenient synthesis of 2-vinyl-substituted 3-cycloalkene-1-carboxylic acid esters

Li²,

Wang³

et al. 2012

Beilstein J. Org. Chem.

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SummaryThe fused 2-vinyl or 2-phenyl substituted cyclobutanones 4 undergo stereoselective ring openings by the action of alkoxide ions (t-BuO− or MeO−) to produce novel vicinally disubstituted cycloalkene derivatives 5 and 6 in moderate to high yields. The ring cleavage usually occurs with complete regioselectivity. The accessibility of γ,δ-unsaturated ester or acid derivatives makes this transformation a good supplementary method for the well-established Johnson–Claisen rearrangement.

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The Use of Bicyclo[3.2.0]heptanones as Versatile Synthons in Organic Chemistry

Cited by 33 publications

References 0 publications

Cyclobutanone Analogues of β‐Lactam Antibiotics: β‐Lactamase Inhibitors with Untapped Potential?

Cyclobutanone Analogues of β‐Lactam Antibiotics: β‐Lactamase Inhibitors with Untapped Potential?

Synthesis of naturally occurring tropones and tropolones

Alkoxide-induced ring opening of bicyclic 2-vinylcyclobutanones: A convenient synthesis of 2-vinyl-substituted 3-cycloalkene-1-carboxylic acid esters

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