83458-91-7Relevant academic research and scientific papers
Gold-Catalyzed Asymmetric Thioallylation of Propiolates via Charge-Induced Thio-Claisen Rearrangement
Kim, Hanbyul,Jang, Jiwon,Shin, Seunghoon
supporting information, p. 20788 - 20795 (2020/11/27)
A gold(I)-catalyzed enantioselective thioallylation of propiolates with allyl sulfides is described. The key mechanistic element is a sulfonium-induced Claisen rearrangement which helps minimize the allyl dissociation and render higher enantioselectivity. This protocol features remarkable scope of the allyl moiety, allowing enantiocontrolled synthesis of all-carbon quaternary centers, and exhibits exceptional functional group compatibility with many Lewis bases and π-bonds. This intermolecular variant of Claisen rearrangement forges both C-S and C-C bonds concomitantly, providing efficient access to interesting optically active organosulfur compounds which can be transformed further through the vinyl sulfide as a functional handle. The rate of the reaction was zeroth order with respect to allyl sulfides, which suggested a reversible inhibition, providing a resting state for the catalyst. The Hammett plot displayed a correlation with σp values, suggesting a turnover-limiting sigmatropic rearrangement where decreased electron-density on sulfur accelerated the rearrangement.
Stereoselective synthesis of dendrodolide-L
Bujaranipalli, Sheshurao,Das, Saibal
, p. 254 - 260 (2017/03/01)
An efficient stereoselective total synthesis of 12-membered macrolide dendrodolide L has been achieved. The key reactions involved are Keck asymmetric allylation, Jacobsen's hydrolytic kinetic resolution, Sharpless asymmetric epoxidation, Mitsunobu reaction and ring-closing metathesis reaction.
A practical total synthesis of (+)-spirolaxine methyl ether
Yadav,Sreenivas,Srinivas Reddy,Subba Reddy
supporting information; experimental part, p. 8307 - 8310 (2011/02/27)
An efficient and practical total synthesis of (+)-spirolaxine methyl ether is described. The phthalide-aldehyde 3 has been prepared via the Diels-Alder reaction between 1,4-unconjugated diene 5 and a long-chain acetylenic dienophile 6. The carbon framework of spiroketal sulfone 4 has been constructed from monobenzyl protected 1,5-pentanediol and the stereochemistry in both the phthalide portion and the spiroketal portion has been established by the Sharpless asymmetric epoxidation.
Enantioselective total synthesis of aigialomycin D
Lu, Jiangping,Ma, Junying,Xie, Xingang,Chen, Bo,She, Xuegong,Pan, Xinfu
, p. 1066 - 1073 (2007/10/03)
An efficient, convergent approach for the total synthesis of aigialomycin D 1 is described. Key features of the synthetic strategy include (a) a Sharpless asymmetric epoxidation reaction and selective opening of a 2,3-epoxy alcohol to elaborate the two hy
Synthesis of diastereomerically and enantiomerically pure 2,3-disubstituted tetrahydrofurans using a sulfoxonium ylide
Schomaker, Jennifer M.,Pulgam, Veera Reddy,Borhan, Babak
, p. 13600 - 13601 (2007/10/03)
Nucleophilic substitution reactions of 2,3-epoxy alcohols, easily prepared via Sharpless asymmetric epoxidation chemistry, offer access to a wide variety of enantiomerically pure compounds. In this communication, we describe the use of a Payne rearrangement to control regioselectivity in the ring-opening of a series of 2,3-epoxy alcohols with dimethylsulfoxonium methylide to yield diastereomerically and/or enantiomerically pure disubstituted tetrahydrofuran rings. The factors influencing the success and substitution pattern of the THF ring products are discussed, including steric, electronic, and solvent effects. Copyright
Construction of polycyclic ring systems fused to cyclobutane by cascade reactions of formyl α,β-unsaturated esters
Ihara,Taniguchi,Tokunaga,Fukumoto
, p. 1405 - 1410 (2007/10/02)
The intramolecular Michael-aldol reaction of methyl 7-formyloct-2-enoate (8) using iodotrimethylsilane (TMSI) and hexamethyldisilazane (TMS)2NH produced the separable diastereoisomeric mixture of bicyclo[3.2.0]heptanes 9 and 10. Treatment of the α,β-unsaturated ester 19 possessing a formylcyclopropane function under the same reaction conditions caused cyclopropane ring opening-Michael aldol reaction to give the bicyclo[3.2.0]heptane 22. The filifolone derivative 31 was synthesized starting from 19 via 22.
γ-Butyrolactone, an Alternative Source of Chiral Iodo Derivatives.
Kermadec, Dominique,Prudhomme, Michelle
, p. 2757 - 2758 (2007/10/02)
An efficient synthesis of (3S) 1,3-di-tert-butyldimethylsilyloxy-6-iodohexane, a chiral iodo derivative useful for the preparation of functionalised 1,7-dioxaspiroundecanes from γ-butyrolactone is described.
The Synthesis of Cembranolide Precursors via Addition of Allylstannanes to Conjugated Aldehydes
Marshall, James A.,DeHoff, Bradley S.
, p. 863 - 872 (2007/10/02)
The Lewis acid promoted addition of functionalized allylstannanes A9, C10, and C11 to a variety of conjugated aldehydes was examined as a possible route to acyclic precursors of macrocyclic diterpenoids.Additions to crotonaldehyde proceeded as expected, g
REDUCTIVE RING OPENINGS OF ALLYL-ALCOHOL EPOXIDES
Finan, James M.,Kishi, Yoshito
, p. 2719 - 2722 (2007/10/02)
Red-Al reduction of allyl-alcohol epoxides was shown to yield 1,3-diols in high regioselectivity, while DIBAL reduction was shown to yield 1,2-diols.
