A Concise Diels−Alder Strategy for the Asymmetric Synthesis of (+)-Albicanol, (+)-Albicanyl Acetate, (+)-Dihydrodrimenin, and (−)-Dihydroisodrimeninol

Henderson, Jeff R.; Parvez, Masood; Keay, Brian A.

doi:10.1021/ol901372m

Cited by 23 publications

(14 citation statements)

References 35 publications

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“…The older approach by Ihara et al2b gave (+)‐albicanol ( 1 ) in 17 steps and 3.3 % overall yield starting from the already enantioenriched Wieland–Miescher ketone. Another protocol starting from β‐ionone was published by Henderson et al,2c and used an auxiliary‐based asymmetric Diels–Alder cycloaddition. In this approach, a chromatographic step was used to separate the albicanol diastereomeric mixture, and 1 could be obtained in 10 steps and 8.5 % overall yield.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of the Sesquiterpenes Albicanol, Drimanol, and Drimanic Acid, and the Marine Sesquiterpene Hydroquinone Deoxyspongiaquinol

Göhl

Seifert

2014

Eur J Org Chem

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A TiIII‐mediated radical cyclization cascade has been used for the synthesis of the sesquiterpenes (+)‐albicanol, (+)‐drimanol, and (+)‐drimanic acid. Starting from all‐trans‐farnesol, (+)‐albicanol could be prepared in seven steps in an overall yield of 14.9 %. Furthermore, a highly diastereoselective hydrogenation of (+)‐albicanol to give (+)‐drimanol has been developed. We used the synthesized (+)‐drimanic acid to achieve the first synthesis of the marine sesquiterpene hydroquinone deoxyspongiaquinol and the quinone deoxyspongiaquinone. Thus, this synthetic strategy gave access to five natural products.

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Section: Introductionmentioning

confidence: 99%

Synthesis of the Sesquiterpenes Albicanol, Drimanol, and Drimanic Acid, and the Marine Sesquiterpene Hydroquinone Deoxyspongiaquinol

Göhl

Seifert

2014

Eur J Org Chem

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“…In the vast majority of cases, these compounds are used as chiral auxiliaries to direct the stereochemical course of transformations such as asymmetric enolate alkylations and aldol reactions. [11] Most of these amino alcohols are present in cyclic systems, an example of which are the oxazolidin-2-ones best known as Evans chiral auxiliaries. [12] These cyclic compounds have been widely reported in the literature to induce high diastereoselectivities in asymmetric alkylations and aldol reactions.…”

Section: Introductionmentioning

confidence: 99%

Recent Developments in Methodology for the Direct Oxyamination of Olefins

Donohoe

Callens

Flores

et al. 2010

Chemistry A European J

267

116

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1,2-Amino alcohols are high-value, versatile functional groups that are found in scores of biologically active molecules and other interesting synthetic targets such as ligands and auxiliaries. Given their prominent position within organic compounds of import, it is no surprise to note that many routes have been developed to access this motif and there are many different starting points from which a synthetic chemist might embark on a synthesis. However, one particular approach stands out from the others, and this is the direct conversion of an alkene to a vicinal amino alcohol derivative (oxyamination). Research in this field has been particularly active in recent years and many interesting new methodologies have been reported. The purpose of this review is to give the reader a tour of the methods that have emerged in the last few years so one can appreciate the myriad of different metals and reagents that can accomplish the oxyamination of alkenes. There are still many challenges to be overcome and, herein, we also outline the areas that are ripe for further development and which bode well for the future.

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“…13e Subsequent indazole addition may occur at either face of the C=C bond of 5 or 7. These four competing pathways all involve six-membered Zimmerman-Traxler-type transition states 14 (TS2a-d). Here, the C−C bond formation and the dissociation of 2,4,6-trimethylbenzoate anion are a concerted process, leading directly to 3H-indazole complexes (8ad), which form the 1H-indazole product upon tautomerization.…”

Section: Resultsmentioning

confidence: 99%

Highly Enantioselective Synthesis of Indazoles with a C3-Quaternary Chiral Center Using CuH Catalysis

Kevlishvili²,

Feng³

et al. 2019

Preprint

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<div><div><div><p>C3-substituted 1H-indazoles are useful and important substructures in many pharmaceuticals. Methods for direct C3- functionalization of indazoles are relatively rare, compared to reactions developed for the more nucleophilic N1 and N2 positions. Herein, we report a highly C3-selective allylation reaction of 1H-N-(benzoyloxy)indazoles using CuH catalysis. A variety of C3-allyl 1H-indazoles with quaternary stereocenters were efficiently prepared with high levels of enantioselectivity. Density functional theory (DFT) calculations suggest that the indazole addition to copper allyl complex proceeds through an enantioselectivity-determining six- membered Zimmerman-Traxler-type transition state. The enantioselectivity is governed both by the ligand-substrate steric interac- tions and the steric repulsions with the pseudoaxial substituent in the six-membered allylation transition state.</p></div></div></div>

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A Concise Diels−Alder Strategy for the Asymmetric Synthesis of (+)-Albicanol, (+)-Albicanyl Acetate, (+)-Dihydrodrimenin, and (−)-Dihydroisodrimeninol

Abstract: A short, mild, highly diastereo-, regio-, and stereoselective Diels-Alder strategy has been developed for the asymmetric synthesis of (+)-albicanol, (+)-albicanyl acetate, (+)-dihydrodrimenin, and (-)-dihydroisodrimeninol.

Cited by 23 publications

References 35 publications

Synthesis of the Sesquiterpenes Albicanol, Drimanol, and Drimanic Acid, and the Marine Sesquiterpene Hydroquinone Deoxyspongiaquinol

Synthesis of the Sesquiterpenes Albicanol, Drimanol, and Drimanic Acid, and the Marine Sesquiterpene Hydroquinone Deoxyspongiaquinol

Recent Developments in Methodology for the Direct Oxyamination of Olefins

Highly Enantioselective Synthesis of Indazoles with a C3-Quaternary Chiral Center Using CuH Catalysis

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