109613-59-4Relevant articles and documents
Ultrasound-accelerated synthesis of chiral allylic alcohols promoted by indium metal
Yadav,Reddy,Srinivasa Reddy
, p. 5333 - 5336 (2003)
The 2-iodomethyl-O-isopropylidine acetals undergo smoothly β-elimination by indium metal in methanol under sonication to afford the corresponding allylic alcohols in excellent yields with high selectivity. This method tolerates both acid and base labile functional and protecting groups and also free hydroxyl groups present in the molecule. Improved yields and enhanced rates are the remarkable features obtained by ultrasound.
An Iterative Phosphate Tether Mediated Approach for the Synthesis of Complex Polyol Subunits
Javed, Salim,Ganguly, Arghya,Dissanayake, Gihan C.,Hanson, Paul R.
supporting information, p. 16 - 21 (2021/12/27)
A pot-economical approach to advanced polyol subunits is reported. The key reactions involved are iterative use of a phosphate tether-mediated one-pot sequential RCM/CM/H2 with subsequent utilization of either a regio-/diasteroselective cuprate addition or a Pd-catalyzed reductive allylic transposition. This method highlights the asymmetric synthesis of 12 complex polyol subunits in 4–6 one-pot sequential operations with a total of 12–14 reactions, of which 4–5 are catalytic, with minimal workup and purification procedures.
Regio- and stereoretentive synthesis of branched, linear (E)- and (Z)-allyl fluorides from allyl carbonates under Ir-catalysis
Benedetto, Elena,Tredwell, Matthew,Hollingworth, Charlotte,Khotavivattana, Tanatorn,Brown, John M.,Gouverneur, Veronique
, p. 89 - 96 (2013/05/09)
This paper describes a new catalytic method for the regio- and stereocontrolled fluorination of allylic carbonates. This transformation uses TBAF·4tBuOH as the fluoride source and [Ir(COD)Cl]2 as the catalyst; the most commonly used [Ir(COD)Cl]2/phosphoramidite system is ineffective. Synthetically, this reaction is characterized by a high degree of structural conservation in going from substrates to the products. The fluorination of (E)-allylic carbonates leading to linear (E)-allylic fluorides (l : b > 20 : 1, E : Z > 20 : 1) is unprecedented and a unique feature of fluoride as the nucleophile. The first examples of transition metal catalyzed fluorination affording (Z)-allyl fluorides (Z : E ratio >20 : 1) are disclosed along with the successful fluorination of branched, linear (E)- and (Z)-allyl carbonates with [18F] fluoride in the presence of [Ir(COD)Cl]2. 18O-Labeling of the reactant reveals internal return during the allylic ionization step, and pathways for effective intra- and intermolecular isotope exchange.
Stereoselective synthesis of tetrahydropyrans through tandem and organocatalytic oxa-Michael reactions: Synthesis of the tetrahydropyran cores of ent-(+)-sorangicin A
Lee, Kiyoun,Kim, Hyoungsu,Hong, Jiyong
, p. 1025 - 1032 (2012/03/27)
Tandem and organocatalytic oxa-Michael reactions of α,β- unsaturated aldehydes were explored for the stereoselective synthesis of structurally complex tetrahydropyrans. Thestereoselective synthesis of 2,6-trans-tetrahydropyrans, which are thermodynamically unfavorable, was accomplished through a reagent-controlled, organocatalytic oxa-Michael reaction. A temperature-dependent configurational switch allowed the preparation of both 2,3-trans-2,6-trans-and 2,3-cis-2,6-cis-tetrahydropyrans from a common substrate. This switch was then used to synthesize the precursors of the C21-C29 and C30-C37 fragments of ent-(+)-sorangicin A. The tandem and organocatalytic oxa-Michael reactions of α,β-unsaturated aldehydes were explored and applied to the stereoselective synthesis of structurally complex tetrahydropyrans. Copyright
