Asymmetric Synthesis of Cyclic Alkenes via Cyclization of Enantioenriched Allylsilanes

Suginome, Michinori; Iwanami, Taisuke; Yamamoto, Akihiko; Ito, Yoshihiko

doi:10.1055/s-2001-14656

Cited by 22 publications

(10 citation statements)

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“…The synthetic utility of the method has been demonstrated by the synthesis of highly enantioenriched, functionalized allylsilanes including those supported on a polymer resin. [31,32] …”

Section: Resultsmentioning

confidence: 98%

Stereoselective Synthesis of Highly Enantioenriched (E)‐Allylsilanes by Palladium‐Catalyzed Intramolecular Bis‐Silylation: 1,3‐Chirality Transfer and Enantioenrichment via Dimer Formation

Suginome

Iwanami

Ohmori

et al. 2005

Chemistry A European J

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Highly enantioenriched (E)-allylsilanes have been synthesized from optically active allylic alcohols on the basis of Pd-catalyzed intramolecular bis-silylation followed by highly stereospecific Si-O elimination reactions. The method involves three steps: 1) O-disilanylation of the allylic alcohols with chlorodisilanes, 2) intramolecular bis-silylation in the presence of a 1,1,3,3-tetramethylbutyl isocyanide/[Pd(acac)2] (acac = acetylacetonate) catalyst at 110 degrees C, and 3) treatment of the reaction mixture with organolithium reagents. The overall transformation proceeds with nearly complete conservation of the enantiopurity of the starting allyl alcohols by transposition of the C=C bond. For instance, (R)-(E)-3-decen-2-ol (99.6-99.7 % ee) produced (S)-(E)-4-(organosilyl)-2-decene of 98.8-99.4 % ee for a variety of silyl groups, including Me3Si, Me2PhSi, tBuMe2Si, Et3Si, and iPr3Si. In the bis-silylation step, the initially formed trans-1,2-oxasiletanes immediately dimerize to stereoselectively give 1,5-dioxa-2,6-disilacyclooctanes, which are isolated in high yield by carrying out the reaction at 70 degrees C. The eight-membered ring compounds undergo thermal extrusion of (E)-allylsilanes in high yield at 110 degrees C, along with formation of 1,3-dioxa-2,5-disilacyclohexane derivatives. These in turn undergo a Peterson-type elimination by treatment with nucleophiles such as BuLi and PhLi to give the (E)-allylsilanes. All of the steps involved in the sequence proceed with extremely high stereoselectivity and stereospecificity, leading to almost complete 1,3-chirality transfer through the overall transformation. The dimerization step, which forms diastereomeric intermediates, allows the synthesis of a highly enantioenriched allylsilane (99.4 % ee) from an optically active allylic alcohol with lower enantiopurity (79.2 % ee) by enrichment of enantiopurity. A general method for the determination of the enantiomeric excesses of (E)-allylsilanes is also described in detail.

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“…The synthetic utility of the method has been demonstrated by the synthesis of highly enantioenriched, functionalized allylsilanes including those supported on a polymer resin. [31,32] …”

Section: Resultsmentioning

confidence: 98%

Stereoselective Synthesis of Highly Enantioenriched (E)‐Allylsilanes by Palladium‐Catalyzed Intramolecular Bis‐Silylation: 1,3‐Chirality Transfer and Enantioenrichment via Dimer Formation

Suginome

Iwanami

Ohmori

et al. 2005

Chemistry A European J

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“…, 3 ) were less well developed. 12 We therefore developed an effective protocol for the synthesis of silanes 3a–3c based on the regioselective addition of Grignard reagent-derived vinylcuprates to trimethylsilylepoxide 14 ( Scheme 2 ). 13 …”

Section: Resultsmentioning

confidence: 99%

Triflimide-catalyzed allylsilane annulations of benzylic alcohols for the divergent synthesis of indanes and tetralins

et al. 2017

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“…Although the silyl‐Prins cyclization has frequently been used to yield pyrans, reported examples of the synthesis of seven‐membered oxacycles by this methodology are rather less common. Suginome and Ito, explored the production of seven‐membered oxacycles in high yields and with excellent diastereoselectivity through reactions between highly enantioenriched allylsilyl alcohols and aldehydes in the presence of TMSOTf. Moreover, the reactions occurred with almost perfect chirality transfer (Scheme ).…”

Section: Synthesis Of Oxacycles By Silyl‐prins Cyclizationmentioning

confidence: 99%

Synthesis of O‐ and N‐Heterocycles by Silyl‐Prins Cyclization of Allylsilanes

Díez-Poza

Barbero

2017

Eur J Org Chem

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Prins cyclization has emerged as one of the most valuable methods for the construction of heterocycles. It proceeds through intramolecular addition of a π‐nucleophile to an oxocarbenium or related ion. The use of electron‐rich alkenes, such as allylsilanes (so‐called silyl‐Prins cyclization) offers the benefit of allowing more selective reactions. The regio‐ and stereochemical outcomes of these transformations are explained by well‐stablished transition states. This review presents the most important contributions involving silyl‐Prins cyclization to the stereoselective preparation of oxygen and nitrogen heterocycles. The influence of different structural variants in the selectivity of the cyclization is discussed. These reactions have frequently been used as key steps in the synthesis of a wide variety of natural products.

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Asymmetric Synthesis of Cyclic Alkenes via Cyclization of Enantioenriched Allylsilanes

Cited by 22 publications

References 1 publication

Stereoselective Synthesis of Highly Enantioenriched (E)‐Allylsilanes by Palladium‐Catalyzed Intramolecular Bis‐Silylation: 1,3‐Chirality Transfer and Enantioenrichment via Dimer Formation

Stereoselective Synthesis of Highly Enantioenriched (E)‐Allylsilanes by Palladium‐Catalyzed Intramolecular Bis‐Silylation: 1,3‐Chirality Transfer and Enantioenrichment via Dimer Formation

Triflimide-catalyzed allylsilane annulations of benzylic alcohols for the divergent synthesis of indanes and tetralins

Synthesis of O‐ and N‐Heterocycles by Silyl‐Prins Cyclization of Allylsilanes

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