Stereoselective Synthesis of (+)-Boronolide

(+)-Boronolide (1) and its deacetylated products have attracted much attention of synthetic chemists due to their diverse biological properties as well as their structural complexities.[1] Many of these reported synthesis involved dehydrogenation of δ-lactone by using benzeneseleninic anhydride or ring-closing olefin metathesis (RCM) to introduce the requisite α,β-unsaturated δ-lactone in boronolide. Here, we report the synthesis of boronolide with diastereoselective propargylation of α-hydroxy aldehyde as the key step and D-gluconolactone as the starting material.     

(S)-(+)-姜黄烯的立体选择性全合成

利用不对称双羟化反应和Raney镍的原位还原,高对映选择性和高产率地实现了(S)-(+)-α-姜黄烯(1)的立体选择性合成.用MsCl保护化合物7a和7b时,发现了有趣的消除和重排反应,得到对应的二烯化合物8.     

Stereoselective Synthesis of (+)-Peperomin C

The stereoselective synthesis of peperomin C is reported. The key steps include the stereoselective alkylation of the substituted diphenylmethyl group to the r-butyrolactone ring and transformation of the carbonyl group to the other side in the butyrolactone ring by reduction of the lactone carbonyl followed by degradative oxidation.     

Stereoselective Total Synthesis of Chrysanthemol

Recently,muchattentionhasbeenpaidtothesynthesisofbioactivenaturalproducts.Chrysanthemol,aneudesmanetypesesquiterpene,firstisolatedfromChrysanthemumindicumL.byD.Q.Yuetal.',showedstrongantiinflanunatoryactivityinmice.ThestructureandabsolutestereochemistryofchrVsanthemolwereelucidatedas1ThesyntheticrouteofchrysanthemolflomR-( )-carvoneisdepictedinScheme1:n.50%aqACOH,2hr;d)KOH,EtOH,oOC,3hr,e)Na,propanol,50"C,6hr,67.2%;66.7%i)m-CPBA/NaHCO3,CHZC12,r.t.,3.5hr,84%;TreatmentofR-( )-carvon…     

Stereoselective Total Synthesis of Rugulactone

The stereoselective synthesis of the naturally occurring dihydropyranone rugulactone has been accomplished starting from 3‐phenylpropan‐1‐ol employing Maruoka allylation and ring‐closing metathesis as the key steps.     

Stereoselective Total Synthesis of Dodoneine

A simple and highly efficient stereoselective total synthesis of dodoneine ( 1 ), a naturally occurring bioactive 5,6‐dihydro‐2H‐pyran‐2‐one, was achieved. The synthesis involved Keck's asymmetric allylation, iodine‐induced electrophilic cyclization, and Grubbs' catalyzed ring‐closing metathesis as key steps.     

烯虫酯的立体选择性全合成

以香茅醛为起始原料, 通过羟醛缩合反应和Reformatskii反应得到3,7,11-三甲基-2,4,10-十二碳三烯酸异丙酯的双键顺反异构体混合物, 经苯硫酚两次催化双键顺反异构化, (2E,4E)-异构体3a的含量由原来的26%提高到85%. 再通过醚化反应, 立体选择性地全合成了具有保幼激素活性的昆虫生长调节剂烯虫酯及其异构体, 即11-甲氧基-3,7,11-三甲基-2,4-十二碳二烯酸异丙酯. 其中具有较高生物活性的(2E,4E)-异构体的含量达85%. 各步所合成的化合物的结构经IR, MS和NMR证实.     

Stereoselective Partial Synthesis of (+)-Pisiferic Acid

(+)-Pisiferic acid ( 1 ), an antibiotic active against Gram-negative and Gram-positive bacteria, was synthesized starting from dehydroabietic acid ( 2 ) or abietic acid ( 26 ). The terpene ring system was functionalized and a Barton reaction used to oxidize Me(20). The intermediates of this photochemical reaction were isolated and characterized.     

Stereoselective Total Synthesis of Botryolide E

The stereoselective total synthesis of the naturally occurring γ‐lactone derivative botryolide E ( 1 ) was accomplished with acetaldehyde as the starting material (Scheme 2). The asymmetric allyl boration, asymmetric dihydroxylation, chelation‐mediated diastereoselective vinylation, and ring‐closing metathesis reaction are the key steps. The method can conveniently be utilized for the preparation of other related γ‐lactone derivatives.     

Stereoselective Total Synthesis of Phenolic Nonadecanediol

A simple and highly efficient synthetic route has been developed for synthesis of 1‐(4‐hydroxyphenyl)nonadecane‐3,5‐diol ( 1 ). The two stereogenic centers were generated by employing proline asymmetric α‐hydroxylation (MacMillan α‐hydroxylation), Jacobsen's hydrolytic kinetic resolution (HKR), and, finally, Yamaguchi oxirane opening as key steps (Scheme 2).     

Stereoselective Total Synthesis of Stagonolide C

A convergent and efficient total synthesis of stagonolide C ( 1 ), a phytotoxic metabolite, was achieved (Schemes 2 and 3) The synthesis exploited the high configuration control in the Prins cyclization along with alkene rearrangement and ring‐closing metathesis as key steps.     

First Stereoselective Total Synthesis of Modiolin

Russian Journal of Organic Chemistry - The first stereoselective total synthesis of the linear pentaketide Modiolin has been performed via Jacobsen’ hydrolytic kinetic resolution and...     

First Stereoselective Total Synthesis of Oplopandiol

The first stereoselective synthesis of the naturally occurring conjugated diyne oplopandiol is reported. The pivotal functionalities are derived from Cadiots? Chodkiewicz cross‐coupling reaction, Ohira? Bestmann alkynation, asymmetric Noyori reduction, and cis‐olefination reaction     

Stereoselective Total Synthesis of Xestodecalactone C

A simple and highly efficient stereoselective total synthesis of xestodecalactone C ( IIb ), a polyketide natural product, was achieved (Scheme 2). The synthesis involved Keck's asymmetric allylation, a iodine‐induced electrophilic cyclization, and an intramolecular Friedel–Crafts acylation as key steps.     

Stereoselective Total Synthesis of Stagonolide E

An efficient and highly stereoselective synthesis of stagonolide E ( 1 ) starting from the readily available hexane‐1,6‐diol ( 8 ) was accomplished, employing MacMillan α‐hydroxylation, Horner? Wadsworth? Emmons olefination, (Z)‐selective Still? Gennari olefination, and Yamaguchi lactonization as key steps.     

A Stereoselective Total Synthesis of Verbalactone

A stereoselective total synthesis of verbalactone has been achieved starting from commercially available hexanal. The sequence involves Maruoka allylation, diastereoselective iodine‐induced electrophillic cyclization, ring opening of epoxide, and Yamaguchi macrolactonization as the key steps.