A Versatile Approach for the Asymmetric Synthesis of 3-Alkyl-isoindolin-1-ones

3 Ｓｕｂｓｔｉｔｕｔｅｄｉｓｏｉｎｄｏｌｉｎ 1 ｏｎｅｓ (2 ,3 ｄｉｈｙｄｒｏ 1Ｈ ｉｓｏｉｎｄｏｌｉｎ 1 ｏｎｅｓ)ｏｆｇｅｎｅｒａｌｓｔｒｕｃｔｕｒｅ (1)ｃｏｎｓｔｉｔｕｔｅｔｈｅｋｅｙｓｔｒｕｃｔｕｒａｌｆｅａｔｕｒｅｏｆａｌａｒｇｅｎｕｍｂｅｒｏｆｂｉｏａｃｔｉｖｅｍｏｌｅｃｕｌｅｓｏｆｎａｔｕｒａｌｏｒｓｙｎｔｈｅｔｉｃｏｒｉｇｉｎ .Ｆｏｒｅｘａｍｐｌｅ ,ｌｅｎｎｏｘａｍｉｎｅ (2 ) ,1ｎｕｅｖａｍｉｎｅａｎｄｃｈｉｌｅｎｉｎｅａｒｅａｌｋａｌｏｉｄｓｉｓｏｌａｔｅｄｆｒｏｍｖａｒｉｏｕｓ…     

Amino Acids as a Chiral Pool: Synthesis of (S)‐and (R)‐2‐N‐Carbomethoxy‐5‐aminoindane from (S)‐ and (R)‐Phenylalanines

Enantioselective syntheses of (R)‐and (S)‐2‐N‐carbomethoxy‐5‐aminoindanes from (R)‐ and (S)‐phenylalanines, respectively, are described. A Friedel–Crafts reaction employing N‐carbomethoxy phenylalanine leads to chiral 2‐N‐carbomethoxy‐1‐indanone, which is diastereoselectively reduced to 1‐hydroxy‐2‐N‐carbomethoxyindane. After protection of the hydroxyl group, a regioselective nitration gives a 6‐nitroindane intermediate, which upon hydrogenation affords (R)‐or (S)‐2‐N‐carbomethoxy‐5‐aminoindane.     

Asymmetric Synthesis of (R)‐(−)‐Rhododendrol,the Aglycone of the Hepatoprotective Agent Rhododendrin

Abstract

Starting from 2,3‐O‐isopropylidene‐D‐glyceraldehyde (3) as chiral material, (R)‐(?)‐rhododendrol 2, the aglycone of the naturally occurring rhododendrin 1 was synthesized.     

Catalytic Approach for the Synthesis of bis‐Calixarenes

Three new tail‐to‐tail linked biscalix[6]arenes joined via ether linkages have been synthesized. These bis calix[6]arenes have been characterized by ¹H NMR, ¹³C NMR, and mass spectroscopy and elemental analysis.     

Versatile Sugar Derivatives for the Synthesis of Potential Degradable Hydrophilic‐Hydrophobic Polyurethanes and Polyureas

Biodegradable polymers obtained from renewable natural sources are currently receiving increasing attention because they are an alternative to the traditional petroleum‐based plastics. In the present communication we describe the synthesis of the diol monomers 2,3,4‐tri‐O‐benzyl‐L‐arabinitol (ABnOH) and 2,3,4‐tri‐O‐benzylxylitol (XBnOH), and the diamino monomers 1,5‐diamino‐1,5‐dideoxy‐2,3,4‐tri‐O‐benzyl‐L‐arabinitol (ABnNH ₂ ) and 1,5‐diamino‐1,5‐dideoxy‐2,3,4‐tri‐O‐benzylxylitol (XBnNH ₂ ), which can be used in the preparation of new potentially biodegradable sugar‐based polymers. As an example, we describe the synthesis and characterization of a polyurethane [PU‐(ABnOH‐HMDI)] and a polyurea [PUR‐(ABnNH₂‐HMDI)] by poly addition reaction of ABnOH and ABnNH ₂ with 1,6‐hexamethylene diisocyanate.      

Asymmetric Total Synthesis of Mansonone P and R

An asymmetric total synthesis of mansonone P and R were achieved, in which introduction of hydroxy substituent at position 2 was performed by Sharpless dihydroxylation of sily enol ether.     

Asymmetric Synthesis of (-)-(2R,3R,6S)-Irnigaine

Introduction　　Asarelativelynewmemberofnaturalalkaloidswith2 ,6 disubstituted 3 piperidinolskeleton ,irnigaine 1wasisolatedfromthetubersofArisarumVulgare (Araceae)in1995byMelhaouiandBode .1Itsstructureandrelativeconfigurationswereelucidatedby1HNMRstudiesandtheabsoluteconfigurationwasproposedonthebasisofitsopti calrotation .1Soonafterthen ,Meyerandhisco workersreportedthefirstsynthesisof (- ) (2R ,3R ,6S) irni gaineandtheconfigurationconfirmation .Althoughtheirsynthesisroutewasshortan…     

Asymmetric Synthesis of （R）- and （S）-Moprolol

A simple and effective procedure for the enantioselective synthesis of （R）- and （S）-moprolol was described. The key step was the asymmetric synthesis of enantiopure （R）- and （S）-guaifenesin, which were synthesized from enantioenriched （R）-3-chloro-l,2-propanediol and （S）-epichlorohydrin via kinetics of hydrolysis resolution of racemic epichlorohydrin by chiral Salen-Co^Ⅲ complex. The e.e. values of both the optical compounds were above 98%, and the chemical structures of the target compounds were confirmed by ^1H NMR, ^13C NMR, IR, and MS.     

An Improved Asymmetric Synthesis of Unusual Amino Acid (2S,3S)‐3‐Hydroxyproline

Abstract

An improved three‐steps method for the conversion of N‐benzyl (S)‐3‐hydroxypyrrolidin‐2‐one 6 to (2S,3S)‐3‐hydroxyproline 1 is reported. The key step is the reductive cyanation of 6. The synthesis of 1 constitutes a formal asymmetric synthesis of (2S,3S)‐3‐hydroxyproline betaines 2.     

Asymmetric Synthesis of (+)‐epi‐Cytoxazone

The asymmetric synthesis of (+)‐epi‐cytoxazone, a stereoisomer of potent cytokine modulator cytoxazone, starting from anisaldehyde in six steps, is described. The required configuration was established via Sharpless kinetic resolution followed by the Mitsunobu reaction.     

A New Approach for Asymmetric Synthesis of （-）-Umbelactone

A concise and efficient total synthesis of (-)-umbelactone 1, an occurring γ-hydroxymethyl-α, β-butenolide from Memycelon umbelatum Burro, is described. The synthesis features the use of a ring closing metathesis strategy.     

Synthesis of Pyrano‐ and Pyrido‐Anellated Pyranosides as Precursors for Nucleoside Analogues

The push‐pull activated methyl (3Z)‐4,6‐O‐benzylidene‐3‐[(methylthio)methylene]‐3‐deoxy‐α‐D‐erythro‐hexopyranosid‐2‐ulose (1) reacted with dialkyl malonate in the presence of potassium carbonate to give the alkyl (2R,4aR,6S,10bS)‐4a,6,8,10b‐tetrahydro‐6‐methoxy‐8‐oxo‐2‐phenyl‐4H‐pyrano[3′,2′:4,5]pyrano[3,2‐d][1,3]dioxine‐9‐carboxylates 2 and 3. Treatment of 1 with 3‐oxo‐N‐phenyl‐butyramide, N‐(4‐methoxy‐phenyl)‐3‐oxo‐butyramide, and 3‐oxo‐N‐o‐tolyl‐butyramide, respectively, in the presence of potassium carbonate and 18‐crown‐6 yielded the (2R,4aR,6S,10bS)‐9‐acetyl‐7‐aryl‐4,4a,7,10b‐tetrahydro‐6‐methoxy‐2‐phenyl[1,3]dioxino‐[4′,5′:5,6]pyrano[3,4‐b]pyridin‐8(6H)‐ones 4–6. (2R,4aR,6S,10bS)‐4,4a,8,10b‐Tetrahydro‐6‐methoxy‐8‐oxo‐2‐phenyl‐4H‐pyrano[3′,2′:4,5]pyrano[3,2‐d][1,3]dioxine‐9‐carboxamide (7) was prepared by anellation reactions of 1 either with malononitrile or with cyanoacetamide.     

Synthesis of (R)‐Japonilure and (4R,9Z)‐9‐Octadecen‐4‐olide,Pheromones of the Japanese Beetle and Currant Stem Girdler

Asymmetric total synthesis of the sex pheromones of Japanese beetle and currant stem girdler, (R)‐japonilure (1) and (4R,9Z)‐9‐octadecen‐4‐olide (2), has been achieved.     

Facile and Versatile Route to the Synthesis of Fused 2‐Pyridones: Useful Intermediates for Polycyclic Sytems

The reaction of various heteroaromatic amino nitriles with diethyl malonate under basic conditions is reported. This reaction affords a series of different highly functionalized 2‐pyridone condensed systems, which can be suitable intermediates in the construction of polyheterocyclic structures.     

Facile Synthesis of (S,S)‐1,2‐Diacylamides and (S,S)‐1,2‐Diamines with C 2‐Symmetry

A series of chiral vicinal tertiary diacylamides with C ₂‐symmetry was synthesized from (S)‐α‐phenylethylamine, different aromatic aldehydes, and oxalyl chloride. The diacylamides obtained were then reduced to afford chiral vicinal diamines with C ₂‐symmetry. We propose that the diacylamides existed in four stable conformational isomers in solution because of the dihedral angle between acylamide bonds.     

Preparation of S‐ and N‐Linked Glycosylated Amino Acid Building Blocks for Solid‐phase Glycopeptide Library Synthesis*

A general route for the preparation of 1,2‐trans‐linked S‐glycosylated amino acid building blocks by a Lewis‐acid‐promoted condensation of peracetylated glycosyl donors and N ^α‐Fmoc‐Cys‐OH, in good overall yield, is described. In addition, a short and time‐efficient route was applied for the synthesis of N‐glycosylated amino acid building blocks in good overall yields by coupling unprotected glycosylamines and N ^α‐Fmoc‐Asp(OH)‐O ^t Bu using TBTU activation.     

Methods for the Preparation of Micro‐ and Nanocrystals of Urethane‐Substituted Polydiacetylenes

Urethane‐substituted polydiacetylene (PDA) crystals of bis(ethyl)‐urethane of 5,7‐dodecadiyne‐1,12‐diol (poly(ETCD)) with micronscale and nanoscale dimension were fabricated by either ultrasonication, surfactant addition or vapor phase processing approaches. Scanning electron microscope (SEM) and transmission electron microscope (TEM) were used to evaluate the sizes and the shapes of the obtained poly(ETCD) microcrystals. Dynamic light scattering (DLS) was performed to investigate in situ size distributions of these crystals in aqueous suspension. A UV/Visible/NIR Spectrometer (UV/Vis/NIR) was used to study the electronic absorption of the poly(ETCD) microcrystals. Thermochromic phenomena for poly(ETCD) crystals still exist after their dimension was decreased to the nanoscale.     

Convenient Synthesis of Pyrrole‐ and Indolecarboxylic Acid tert‐Butylesters

Abstract

The tert‐butylesters of pyrrole‐ and indolecarboxylic acids are readily accessed by reacting the appropriate carboxylic acids with N,N‐dimethylformamide di‐tert‐butyl acetal.     

Synthesis of 4‐Substituted‐ and 1,4‐Disubstituted‐4‐Hydroxypyrrolidin‐2‐ones

This report describes the synthesis of 4‐substituted‐ and 1,4‐disubstituted‐4‐hydroxypyrrolidin‐2‐ones by cyclization of intermediate γ‐aminoesters prepared from alkylbenzylamines, α‐bromoketones, and lithio ethyl acetate.