Transformation of carboxylic acid esters into 2-substituted allyl halides through tertiary cyclopropyl sulfonates. Application in the synthesis of (±)-ipsenol and (±)-ipsdienol, components of Ips typographus spark beetle pheromone

Matyushenkov, E. A.; Kulinkovich, O. G.

doi:10.1134/s1070428006040038

Cited by 7 publications

(4 citation statements)

References 15 publications

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“…The solvents used were dried according to standard procedures and distilled. [8], 18.7 g (99.2 mmol), was dissolved in 100 ml of benzene, 20.9 ml (150 mmol) of triethylamine and 16.2 g (109 mmol) of phthalic anhydride were added, and the mixture was heated for 45 min under reflux in an argon atmosphere, cooled, and treated with 200 ml of 10% H 2 SO 4 . The organic layer was separated, the aqueous layer was extracted with 100 ml of benzene, the extract was combined with the organic phase, washed with a saturated solution of sodium chloride, dried over MgSO 4 , and evaporated under reduced pressure to isolate 34.5 g of crude hydrogen phthalate IV as a viscous oily substance.…”

Section: Methodsmentioning

confidence: 99%

“…We previously described [8] an efficient synthesis of racemic ipsdienol (I) starting from accessible ethyl 3-chloropropionate via titanium-catalyzed cyclopropanation according to Kulinkovich [9], subsequent cationic cyclopropyl-allyl isomerization of cyclopropanol II methanesulfonate into 2-chloroethyl-3-bromoprop-1-ene [10], and condensation of the latter with prenal in the presence of zinc (Scheme 1). Alcohol III thus obtained was converted into ipsdienol (I) by protection of the hydroxy group and dehydrochlorination.…”

Section: Methodsmentioning

confidence: 99%

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Stereoselective synthesis of (R)- and (S)-Ipsdienols, pheromone components of bark beetles of the Ips family

Kovalenko

Matyushenkov

2012

Russ J Org Chem

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R)-and (S)-Ipsdienols, components of pheromones of bark beetles of the Ips family, were synthesized with high enantiomeric purity (>98%) from 8-chloro-2-methyl-6-methylideneoct-2-en-4-ol prepared from ethyl 3-chloropropionate via cyclopropanation according to Kulinkovich. 8-Chloro-2-methyl-6-methylideneoct-2-en-4-ol was converted into the corresponding hydrogen phthalate whose stereoisomeric salts with (R)-and (S)-1-phenylethanamines were separated by crystallization, and subsequent hydrolysis of the latter and dehydrohalogenation with potassium tert-butoxide gave targeted (R)-and (S)-ipsdienols. Scheme 1.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Stereoselective synthesis of (R)- and (S)-Ipsdienols, pheromone components of bark beetles of the Ips family

Kovalenko

Matyushenkov

2012

Russ J Org Chem

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“…Following a similar protocol, 8‐chloro‐2‐methyl‐6‐methyleneoct‐2‐en‐4‐ol ( 38 ) gave ipsdienol ( II ) in 60 % overall yield (Scheme 15). [51] …”

Section: Synthesis Of (±)‐Ipsenol and (±)‐Ipsdienolmentioning

confidence: 99%

“…( S )‐(+)‐Ipsdienol ( II ) was synthesized in high enantiomeric purity (>98 %) from the corresponding hydrogen phthalate of 8‐chloro‐2‐methyl‐6‐methyleneoct‐2‐en‐4‐ol ( 38 ) (Scheme 15), [51] whose diastereoisomeric salt with ( R )‐1‐phenylethanamine was separated and isolated by crystallization, submitted to hydrolysis, and dehydrohalogenation with tert ‐BuOK [95] . The ee value of ( S )‐(+)‐ II was determined as usual in the 1 H NMR spectrum of its MTPA ester.…”

Section: Synthesis Of Enantiomerically Pure Ipsenol and Ipsdienolmentioning

confidence: 99%

The Synthesis of Ipsenol and Ipsdienol: A Review (1968–2020)

Marco‐Contelles

2021

The Chemical Record

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Herein I present a review on the synthesis of ipsenol and ipsdienol, two aggregation pheromones of bark beetles, isolated from different species of genus Ips, and serious pests of conifer forests. I have covered the literature for around fifty years, since 1968 to 2020. This account has been divided in different sections and sub‐sections, including a general and brief outlook on their isolation, structure and biological activity, to continue with the reported synthesis of racemic ipsenol and ipsdienol, including my own contribution to topic, and the presentation of reports describing the synthesis of enantiomerically pure ipsenol and ipsdienol. Particular attention has been devoted to identify and highlight racemic or enantiomerically pure “isoprene synthons”, and isoprenylation methods employed in the synthesis of ipsenol and ipsdienol, of general interest for related terpene derivatives synthesis.

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The Kulinkovich Cyclopropanation of Carboxylic Acid Derivatives

Kun

Kulinkovich

2012

Organic Reactions

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Cyclopropanes are characterized by high ring‐strain energy and have been employed as useful building blocks in organic synthesis. The incorporation of a heteroatom donor substituent such as OH, OR, NR2, or SR on the ring imparts enhanced reactivity. Hydroxycyclopropanes (cyclopropanols) in particular have been thoroughly studied due to their facile ring cleavage. Among several known methods, a new method for preparation of cyclopropanols involves dialkoxytitanacyclopropane‐mediated cyclopropanation (the Kulinkovich cyclopropanation) of esters with Grignard reagent in the presence of titanium isopropoxide. The striking feature of this method is the facile formation of a three‐membered ring from a simple Grignard reagent which acts as a 1,2‐dicarbanion equivalent through a pivotal dialkoxytitana‐cycloproapne intermediate. These reactions benefit from the availability of inexpensive reagents, ease of operation, and high selectivity for cis ‐dialkylcyclopropanols. This cyclopropanation reaction has since been extended to other carboxylic derivatives to provide convenient access to several heteroatom‐substituted cyclopropanes. The objective of this chapter is to provide an updated, comprehensive coverage of the literature on the Kulinkovich cyclopropanation reaction and related processes. Key mechanistic issues are summarized.

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Transformation of carboxylic acid esters into 2-substituted allyl halides through tertiary cyclopropyl sulfonates. Application in the synthesis of (±)-ipsenol and (±)-ipsdienol, components of Ips typographus spark beetle pheromone

Cited by 7 publications

References 15 publications

Stereoselective synthesis of (R)- and (S)-Ipsdienols, pheromone components of bark beetles of the Ips family

Stereoselective synthesis of (R)- and (S)-Ipsdienols, pheromone components of bark beetles of the Ips family

The Synthesis of Ipsenol and Ipsdienol: A Review (1968–2020)

The Kulinkovich Cyclopropanation of Carboxylic Acid Derivatives

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