Stereoselective Synthesis of Acetoacetate-Derived Enol Triflates

Babinski, David J.; Soltani, Omid; Frantz, Doug E.

doi:10.1021/ol8010002

Cited by 70 publications

(82 citation statements)

References 34 publications

(14 reference statements)

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“…LiOH under biphasic conditions. 18 While similar methylation reactions could be catalyzed by Fe(acac) 3 in high yield, 19 significant isomerization of the alkene was observed under Fe-catalysis. A reduction/oxidation sequence of ester 21 by DIBAL-H/Dess-Martin periodinane gave alde-hyde 22 which was subjected to the Nagao-Fujita aldol protocol to give 23 with excellent diastereoselectivity (>20:1, based on 1 H NMR).…”

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confidence: 97%

Total Synthesis of the Potent cAMP Signaling Agonist (−)-Alotaketal A

et al. 2012

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We developed a convergent synthetic route to the potent cAMP signaling agonist (−)-alotaketal A employing two stages of SmI2-mediated reductive allylation reactions for assembling the polycycle and fragment coupling. Also notable are a Hg(OAc)2-mediated selective alkene oxidation and the subtlety for formation of the unprecedented spiroketal ring system. The AKAR4 and ICUE3 probes were used to evaluate the cAMP singaling agonistic activity of (−)-alotaketal A and elucidate its structure-activity relationship.

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confidence: 97%

Total Synthesis of the Potent cAMP Signaling Agonist (−)-Alotaketal A

et al. 2012

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“…Next, ( Z ) and ( E ) acyclic enol triflates were stereoselectively synthesized using modular acetoacetate derivatives and applied to the relay Heck reaction. 19 Although these alkenyl triflates were found to be less reactive, raising the temperature to room temperature provided the products in modest yields and good enantioselectivity ( 4g, 4h, 4i ). The geometry of the alkene was preserved during the course of the reaction, showcasing the potential utility of this process.…”

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confidence: 99%

Palladium-Catalyzed Enantioselective Heck Alkenylation of Acyclic Alkenols Using a Redox-Relay Strategy

2015

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We report a highly enantioselective intermolecular Heck reaction of alkenyl triflates and acyclic primary or racemic secondary alkenols. The mild reaction conditions permit installation of a wide range of alkenyl groups at positions β, γ or δ to a carbonyl group in high enantioselectivity. The success of this reaction is attributed to the use of electron-withdrawing alkenyl triflates, which offer selective β-hydride elimination followed by migration of the catalyst through the alkyl chain to give the alkenylated carbonyl products. The synthetic utility of the process is demonstrated by a two-step modification of a reaction product to yield a tricyclic core structure, present in various natural products.

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“…To this end, distannane 17 was prepared as described by Mitchell et al [10] The required triflates 16 [11] and 18 [12] were prepared according to literature procedures in 81 % and 61 % yield, respectively. Stille coupling of distannane 17 with triflate 18 afforded stannane 20 as a 2:3 mixture of E and Z isomers.…”

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confidence: 99%