Chemoenzymatic route to various spirocyclic compounds based on enantiomerically enriched tertiary allylic, homoallylic, and homopropargylic alcohols

Date

2014-04-30

Author

Tanyeli, Cihangir

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

183
views

0
downloads

A ring closing metathesis (RCM) reaction of dienes and an intramolecular Pauson-Khand (PKR) reaction of enynes derived from tertiary allyl, homoallyl, and homopropargyl alcohol backbones to afford the corresponding spirocyclic dihydrofuran and dihydropyrans and spirocyclic cyclopentenone pyrans, respectively, are described. Cyclopent-2-ene anchored tertiary allyl, homoallyl, and homopropargyl alcohols la-c have been efficiently resolved via enzymatic resolution with high ee (up to 90%) with 44%, 40%, and 43% chemical yields, respectively. Moreover, the cyclohex-2-ene anchored tertiary allyl, homoallyl, and homopropargyl alcohols 3a-c have also been resolved in the same manner with high ee (up to 97%) and in 42%, 45%, and 49% chemical yields. Enantiomerically enriched dienes derived from tertiary homoallyl alcohols yield the corresponding enantiomerically enriched spirocyclic dihydropyran derivatives via RCM with 74% and 78% chemical yields and with 90% and 97% ee, respectively. Moreover, enantiomerically enriched enynes derived from tertiary homoallyl alcohols afford the corresponding enantiomerically enriched cyclopentenone pyrans with spirocyclic motifs via PKR with 80% and 81% chemical yields, respectively, and as single diastereomers.

Subject Keywords

Physical and Theoretical Chemistry, Inorganic Chemistry, Organic Chemistry, Catalysis

URI

https://hdl.handle.net/11511/40823

Journal

TETRAHEDRON-ASYMMETRY

DOI

https://doi.org/10.1016/j.tetasy.2014.03.004

Collections

Department of Chemistry, Article

Suggestions

OpenMETU
Core

Stereoselective synthesis of optically active dihydrofurans and dihydropyrans via a ring closing metathesis reaction ÇAYİR, Merve; Demirci, Sema; Sezer, Serdar; Tanyeli, Cihangir (Elsevier BV, 2011-06-15) A ring closing metathesis reaction of dienes and a ring closing enyne metathesis reaction derived from allyl, homoallyl and homopropargyl alcohol backbones are described. 2-Heteroaryl substituted allyl, homoallyl and homopropargyl alcohols have been easily and efficiently resolved through enzymatic resolution with high ee (93-99%) and known stereochemistry. Enantiomerically enriched dienes derived from allyl and homoallyl alcohols afforded the corresponding enantiomerically enriched dihydrofuran and dihydro...
Conformational control on remote stereochemistry in the intramolecular Pauson-Khand reactions of enynes tethered to homoallyl and homopropargyl alcohols Sezer, Serdar; Ozdemirhan, Devrim; Sahin, Ertan; Tanyeli, Cihangir (Elsevier BV, 2006-11-17) An intramolecular Pauson-Khand reaction of enynes derived from homoallyl and homopropargyl alcohols is described. 2-Furyl substituted homoallyl and homopropargyl alcohols are easily and efficiently resolved through enzymatic resolution in a high ee (93-99%) with a known stereochemistry. Each enantiomerically enriched enyne affords the conformationally most stable diastereomeric cyclopenta[c]pyran ring system.
Stereoselective synthesis of optically active cyclopenta[c]pyrans and cyclopenta[c]furans by the intramolecular Pauson-Khand reaction Sezer, Serdar; ŞAHİN, Ertan; Tanyeli, Cihangir (Elsevier BV, 2010-03-16) An intramolecular Pauson-Khand reaction of enynes derived from homoallyl, homopropargyl, and allyl alcohols is described. 2-Heteroaryl-substituted homoallyl, homopropargyl, and allyl alcohols are easily and efficiently resolved through enzymatic resolution in high ee (91-99%) and with a known stereochemistry. Each enantiomerically enriched enyne derived from homoallyl and homopropargyl alcohols affords the conformationally most stable diastereomeric cyclopenta[c]pyran ring system as the sole product, wherea...
Enantioselective synthesis of both enantiomers of 2-amino-2-(2-furyl)ethan-1-ol as a flexible building block for the preparation of serine and azasugars Demir, Ayhan Sıtkı; Sesenoglu, O; Aksoy-Cam, H; Kaya, H; Aydogan, K (Elsevier BV, 2003-05-16) The selective conversion of 1-(2-furyl)-2-hydroxyethan-1-one and ethyl 2-(2-furyl)-2-oxo acetate into (E)- and (Z)-oximes and oxime ethers followed by oxazaborolidine-catalyzed enantioselective reduction using different amino alcohols furnished both enantiomers of the important chiral building block 2-amino-2-(2-furyl)ethan-1-ol with an ee of up to 96%.
Chemoenzymatic synthesis of enantiomerically enriched 2-oxobicyclo[m.1.0]alkan-3-yl acetate derivatives ÖZDEMİRHAN, FAZİLET DEVRİM; ÇELİK, MURAT; ATLI, SELİN; Tanyeli, Cihangir (Elsevier BV, 2006-01-23) Racemic alpha'-acetoxy alpha,beta-unsaturated cyclopentanone and cyclohexanone have been resolved into the corresponding enantiomerically enriched alpha'-hydroxylated and acetoxylated compounds with 96-97% ee via PLE hydrolysis. Stereoselectivity in the palladium(II)-catalyzed reaction between the enantiomerically enriched alpha'-acetoxylated compounds and diazomethane has been investigated. In the alpha'-acetoxylated cyclopentenone, preferential cyclopropanation occurs in the anti-form, whereas alpha'-acet...

Citation Formats

C. Tanyeli, “Chemoenzymatic route to various spirocyclic compounds based on enantiomerically enriched tertiary allylic, homoallylic, and homopropargylic alcohols,” TETRAHEDRON-ASYMMETRY, pp. 658–666, 2014, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/40823.