52461-05-9Relevant academic research and scientific papers
Short synthesis of (+)-aspicillin via asymmetric hexahydroxylation of a triene
Sinha,Keinan
, p. 949 - 951 (1994)
Asymmetric synthesis of the 18-membered lichen macrolide (+)-aspicilin has been achieved in 14 steps and 11% overall yield, starting from an achiral hydrocarbon, (3E)-hexadeca-1,3,15-triene. All four stereogenic carbinol centers have been introduced by three Sharpless asymmetric dihydroxylation (AD) reactions, using both AD-mix-β and AD-mix-α to produce the hexol with very high regio- and enantioselectivity (epimeric excess of 88% at position 2, 96% at positions 3 and 4, and 86% at position 15).
Total Synthesis of the Macrolide (+)-Aspicilin by an Asymmetrically Catalyzed Macrocyclization of an ω-Alkynal Ester
Oppolzer, Wolfgang,Radinov, Rumen N.,Brabander, Jef De
, p. 2607 - 2610 (1995)
ω-Alkynal ester 3, prepared from (S)-propylene oxide 4, yields the macrocyclic (6R)-allylic alcohol 2 (60percent yield, 83percent d.e.) in one operation via monohydroboration, boron/zinc-transmetalation and (-)-DAIB "catalyzed" intramolecular alkenylzinc/aldehyde addition.Introduction of the C(2)-C(3) double bond by selenoxide elimination (2 -> 8), hydroxy-directed epoxidation (8 -> 9), acetate assisted α-epoxide opening (10 -> 12) and acidic methanolysis provides pure (+)-aspicilin (1) in 22percent yield from 4.
Chiral synthesis of (+)-aspicilin by using a furyl group as the masked γ-oxo-α,β-unsaturated carboxylic acid
Kobayashi, Yuichi,Nakano, Miwa,Okui, Hiroki
, p. 8883 - 8886 (1997)
Synthesis of (+)-aspicilin is described. The decisive steps are the diastereoselective dihydroxylation of the key intermediate 2, the subsequent furan ring oxidation, and the chelation-controlled reduction of ketone 1.
A short and efficient stereoselective synthesis of the polyhydroxylated macrolactone (+)-aspicilin
Dixon, Darren J.,Foster, Alison C.,Ley, Steven V.
, p. 123 - 125 (2000)
(equation presented) A short and efficient synthesis of the polyhydroxylated macrolactone (+)-aspicilin 1 using a stereoselective lithium perchlorate mediated addition of allyltributyltin to the equatorially disposed carboxaldehyde of 3 (derived from (R′,R′,R′,S) butane diacetal protected butane tetrol 2) as the key step is described. Terminal group manipulation and Masamune-Roush olefination using phosphonate ester 4 followed by macrocyclization via ring closing metathesis afforded the natural product after partial hydrogenation and global deprotection.
Alternative total synthesis of (+)-aspicilin
Musulla, Sridhar,Bharathi Kumari,Madala, Mahesh,Srinivasa Rao,Naresh, Vema Venkata
, p. 1657 - 1662 (2018/06/15)
The total synthesis of an 18-membered polyhydroxylated macrolide (+)-Aspicilin was accomplished starting from commercially available enantiopure propylene oxide and D-(+)-gluconolactone by asymmetric synthetic approach. The key reactions involved are Witt
Wittig Cyclization of ω-Hydroxy Hemiacetals: Synthesis of (+)-Aspicilin
Schmidt, René,Ostermeier, Michael,Schobert, Rainer
, p. 9126 - 9132 (2017/09/11)
The polyhydroxylated 18-membered lichen macrolide (+)-aspicilin was synthesized in 12 steps and 17% yield (longest linear sequence) starting from d-mannose and (S)-propylene oxide as the source of the stereogenic centers. Key steps were a palladium-catalyzed Csp3X-Csp3ZnX Negishi cross-coupling affording an ω-hydroxy hemiacetal which was macrocyclized via a domino addition-Wittig olefination reaction with the cumulated ylide Ph3PCCO. This synthetic approach also allowed a regioselective glycosylation of 6-OH of aspicilin with d-desosamine, a quick entry to chimeric macrolides with potential antibiotic activity.
'Chiron' approach to the total synthesis of macrolide (+)-Aspicilin
Saidhareddy, Puli,Ajay, Sama,Shaw, Arun K.
, p. 4253 - 4259 (2014/01/17)
An efficient total synthesis of 18 membered macrolactone, (+)-Aspicilin (lichen macrolide) has been achieved in 12 linear steps with 10.2% overall yield from carbohydrate based building block d-glucal. Highlights of the strategy include preparation of 2-deoxysugar from protected glycal 14, two-carbon Wittig olefination of the Swern oxidised intermediate 7, union of 'carbohydrate based' fragment 5 and a long chain (C-11) chiral alcohol 6 by Yamaguchi esterification and finally ring closing metathesis of the resulting compound 4.
Total synthesis of (+)-aspicilin by an alkyne-based approach and its biological evaluation
Raji Reddy, Chada,Rao, Nagavaram Narsimha,Sujitha, Pombala,Kumar, Chityal Ganesh
, p. 1819 - 1824 (2012/05/20)
The stereoselective total synthesis of (+)-aspicilin is described. The pivotal step in this approach is the generation of an enyne intermediate by the coupling of an alkyne with vinyl iodide, which constructed the C6-C7 bond. Conversion of the enyne to th
Asymmetric synthesis of (+)-aspicilin
Wang, Chun-Yi,Hou, Duen-Ren
, p. 389 - 393 (2012/08/08)
Aspicilin (1), an eighteen membered macrolide with four stereocenters, was synthesized using (3R,4R)- 1,5-hexadiene-3,4-diol and (S)-propylene oxide as the starting materials. Sharpless epoxidation on the protected dienediol generated the required three c
Total synthesis of (+)-aspicilin from D-mannitol
Yadav,Rao, T. Srinivasa,Ravindar,Reddy, B. V. Subba
scheme or table, p. 2828 - 2830 (2010/03/03)
The total synthesis of the 18-membered lichen macrolide, (+)-aspicilin, has been accomplished utilizing the Swern oxidation, Masamune-Roush olefination, and ring-closing metathesis of a trienic ester as key steps. d-Mannitol has been utilized as the chiral pool material for the construction of the olefinic aldehyde and the Jacobsen hydrolytic kinetic resolution has been employed for the construction of the olefinic phosphonate ester.
