Stereochemical evidence of dual chemoreceptors for an achiral sex pheromone in Lepidoptera

Chapman, O. L.; Mattes, K. C.; Sheridan, Robert S.; Klun, J. A.

doi:10.1021/ja00483a039

Cited by 77 publications

(11 citation statements)

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“…Chapman et al obtained optically pure (−)‐( S )‐ and (+)‐( R )‐ 4 from the racemic mixture of the compound by recrystallization of diastereoisomeric salts with (−)‐ and (+)‐α‐phenylethylamine, respectively 5. The yield of this resolution, which required numerous crystallizations, was only 4%.…”

Section: Resultsmentioning

confidence: 99%

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Syntheses of Enantiomerically Pure Cyclopent‐2‐ene‐1‐carboxylic Acid and (Cyclopent‐2‐enyl)acetic Acid by Enantioselective Palladium‐Catalyzed Allylic Alkylations − Synthesis of Enantiomerically Pure (−)‐Chaulmoogric Acid

et al. 2003

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Asymmetric Pd-catalyzed allylic alkylations of dimethyl malonate and diethyl 2-acetoxymalonate with 3-chlorocyclopentene, using phosphanyloxazolines 1 and ent-1 as chiral ligands, gave products (−)-2 and (+)-3b with 95 and 99.5% ee, respectively. Oxidative degradation of (+)-3b furnished (+)-(R)-cyclopent-2-ene-1-carboxylic acid [(+)-4] with Ͼ 99% ee. Alkylation product (−)-2 was transformed into enantio-

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Section: Resultsmentioning

confidence: 99%

“…Kugelrohr distillation (5 Torr/90 °C) yielded (+)‐ 4 as a colorless oil (1.03 g, 92%). [α] D 26 = +260.0 ( c = 1.3, CHCl 3 ), {ref 5…”

Section: Methodsmentioning

confidence: 99%

Syntheses of Enantiomerically Pure Cyclopent‐2‐ene‐1‐carboxylic Acid and (Cyclopent‐2‐enyl)acetic Acid by Enantioselective Palladium‐Catalyzed Allylic Alkylations − Synthesis of Enantiomerically Pure (−)‐Chaulmoogric Acid

et al. 2003

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“…The first sequence to butenolide 7 is shown in Scheme 3 and was first developed in the racemic series. After protection of 6-bromohexan-1-ol (8) 13 as the tert -butyldimethylsilyl ether 9 (95% yield), 14 the latter is converted to the alkynyl ester 11 via a three-step sequence. Reaction with ethynyllithium/ethylenediamine complex in dimethyl sulfoxide gives 10 (92% yield).…”

Section: Methodsmentioning

confidence: 99%

“…MS: m/z (rel.intensity, %) = 234 ([M] +. , 6), 219 (3), 216 (16), 190 (31), 173 (10), 161 (100), 145 (18), 133 (21), 105 (32), 91 (70), 77 (25), 65 (13), 43 (16). 1 H NMR (500 MHz, CDCl 3 ): endo-adduct 5: δ = 1.10-1.40 (m, 3 H), 1.41 (d, 3…”

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confidence: 99%

Studies Directed Towards the Total Synthesis of (+)-Himbacine

Hofman¹

1998

Synthesis

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A convergent strategy towards himbacine (1) , involving a Julia coupling between aldehyde 5 and sulfone 6 was found to be ineffective. The aldehyde 5 was synthesized via the thermal intramolecular cycloaddition of 4 with preferred formation of the endo -adduct. The Diels-Alder precursor 4 was obtained from butenolide 7 , the result of a single-step condensation between the enoate derived from the ( Z )-conjugated olefin 12 and 2-acetoxypropanal. In the context of the synthesis of sulfone 6 Taber's method for the synthesis of 2,6-trans -disubstituted piperidine was adapted towards a large scale synthesis of 49 , a useful intermediate for the synthesis in this area.Himbacine (1) was first isolated in 1956 from the bark of Galbulimima baccata , a tree encountered in New Guinea and in parts of Australia. 1 A series of related alkaloids, including himbeline (2) and himgravine (3) , have also been isolated from the same source. 2 The relative and absolute configuration of 1 were determined via an X-ray diffraction study of the corresponding hydrobromic salt. 3 Interestingly, himbacine (1) is a potent muscarinic receptor antagonist that displays selectivity for the M 2 receptor. 4 As such it could become an important lead structure in the development of drugs for the treatment of Alzheimer's disease. 5For a synthetic chemist himbacine (1) possesses an attractive structure. Its skeleton consists of a trans -fused perhydronaphthalene with a cis -fused γ -lactone, the ABC-ring part of the molecule, to which is connected, via a ( E )-double bond, the N -methyl piperidine D-ring. A convergent strategy calls for a coupling of both parts via appropriate ( E )-olefination methodology. The two parts further possess an interesting stereochemical pattern: in the ABCring part six contiguous stereocentres are present, while the D-ring consists of a 2,6-trans -disubstituted piperidine ring.The first total syntheses of (+)-himbacine were described by the groups of Hart for the construction of the ABC-ring system, different intramolecular Diels-Alder strategies with formation of five stereogenic centres (Scheme 1). In the first strategy endo -cycloaddition involving approach of an ( E )-dienophile to the least hindered side of the diene leads to an adduct with the correct stereogenicity at centres C-3, 8, 9, 10 and 11. 6 In the second strategy the exo -cycloaddition involving reaction of the diene to the least hindered side of the ( Z )-dienophile gives an adduct possessing the correct stereochemistry at C-8, 9, 10 and 11 with the further possibility of facile epimerisation at C-1. 7 It is interesting to note that in the same period (1995) independent studies were also reported from this laboratory and by Baldwin and co-workers that follow the first Diels-Alder approach. 8,9 Since the reduction of himgravine (3) to himbacine (1) is a known process, 10 the choice of this particular strategy is a very logical one. In the present paper we would like to describe in detail the work we performed along this line.The convergent route that we...

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“…The fatty acids obtained from this oil are a mixture of 2-cyclopentene-1-undecanoic acid (hydnocarpic acid, 50%), 13-(2-cyclopentene-1-yl) 6-tridecenoic acid (gorlic acid, 10%) and 2-cyclopentene-1-tridecanoic acid (chaulmoogric acid, 32%) (2,3). Chaulmoogra oil and its derivatives show biological activity (4,5) and have great medicinal value (6), especially in the treatment of leprosy (7,8). Some derivatives are also used as an intermediate in the preparation of perfumery compounds (9,10).…”

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Synthesis of dimer and oligomers from (R)‐methyl hydnocarpate

Malkar

Vaidya

Kumar³

2000

J Americ Oil Chem Soc

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We report synthesis and characterization of dimer and oligomer acids from chaulmoogra oil. (R)-Methyl hydnocarpate (methyl ester of the major fatty acid component of chaulmoogra oil) was brominated to give threo-2,3-dibromocyclopentane-1-methyl undecanoate. Formation of two diastereoisomers, viz., threo-2(R),3(R)-dibromocyclopentane-1(R)-methyl undecanoate and threo-2(S),3(S)-dibromocyclopentane-(R)-1-methyl undecanoate, was observed. Dehydrobromination of bromo derivatives using alcoholic KOH gave a cyclopentadiene derivative as intermediate, which underwent Diels-Alder reaction to give dimer and oligomer fatty acids. The products were characterized by ultraviolet, direct exposure probe-mass spectroscopy, 1 H nuclear magnetic resonance (NMR), and 13 C NMR spectroscopic techniques.

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Stereochemical evidence of dual chemoreceptors for an achiral sex pheromone in Lepidoptera

Cited by 77 publications

References 14 publications

Syntheses of Enantiomerically Pure Cyclopent‐2‐ene‐1‐carboxylic Acid and (Cyclopent‐2‐enyl)acetic Acid by Enantioselective Palladium‐Catalyzed Allylic Alkylations − Synthesis of Enantiomerically Pure (−)‐Chaulmoogric Acid

Syntheses of Enantiomerically Pure Cyclopent‐2‐ene‐1‐carboxylic Acid and (Cyclopent‐2‐enyl)acetic Acid by Enantioselective Palladium‐Catalyzed Allylic Alkylations − Synthesis of Enantiomerically Pure (−)‐Chaulmoogric Acid

Studies Directed Towards the Total Synthesis of (+)-Himbacine

Synthesis of dimer and oligomers from (R)‐methyl hydnocarpate

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