Synthesis of (2S,3S)-3'-fluoroisoleucine

The fluorinated amino acid, (2S,3S)-3'-fluoroisoleucine 3, has been synthesised by a route involving stereoselective cuprate or photochemical addition to the compound 4, derived in turn from (2S)-pyroglutamic acid. This provides a reporter group for the hydrophobic amino acid (2S)-isoleucine for use in protein studies.     

Asymmetric synthesis of anti-(2S,3S)- and syn-(2R,3S)-diaminobutanoic acid

Conjugate addition of homochiral lithium N-benzyl-N-alpha-methylbenzylamide to tert-butyl (E)-cinnamate or tert-butyl (E)-crotonate and in situ amination with trisyl azide results in the exclusive formation of the corresponding 2-diazo-3-amino esters in > 95% de. Amination of the lithium (E)-enolates of tert-butyl (3S,alphaR)-3-N-benzyl-N-alpha-methylbenzylamino-3-phenylpropanoate or tert-butyl (3S,alphaS)-3-N-benzyl-N-alpha-methylbenzylaminobutanoate with trisyl azide gives the (2R,3R,alphaR)- and (2S,3S,alphaS )-anti-2-azido-3-amino esters in good yields and in 85% de and > 95% de respectively. Alternatively, tert-butyl anti-(2S,3S,alphaS)-2-hydroxy-3-N-benzyl-N-alpha-methylbenzylaminobutanoate may be converted selectively to tert-butyl anti-(2S,3S,alphaS)-2-azido-3-N-benzyl-N-alpha-methylbenzylaminobutanoate by aziridinium ion formation and regioselective opening with azide. Deprotection of tert-butyl (2S,3S,alphaS)-2-azido-3-aminobutanoate via Staudinger reduction, hydrogenolysis and ester hydrolysis furnishes anti-(2S,3S)-diaminobutanoic acid in 98%, de and 98% ee. The asymmetric synthesis of the diastereomeric syn-(2R,3S)-diaminobutanoic acid (98% de and 98% ee) was accomplished via functional group manipulation of tert-butyl anti-(2S,3S,alphaS)-2-hydroxy-3-N-benzyl-N-alpha-methylbenzylaminobutanoate in a protocol involving azide inversion of tert-butyl (2S,3S)-2-mesyloxy-3-N-Boc-butanoate and subsequent deprotection.     

Synthesis of (2S,3R)-[3',3',3'-2H3]-valine and (2S,3S)-4-fluorovaline

A new synthesis of (2S,3R)-[3',3',3'-2H3]-valine has been completed and (2S,3S)-4-fluorovaline has been synthesised for the first time. Both compounds have been prepared by routes involving stereoselective addition to the (S)-pyroglutamate derivative and are available for studies in several areas of bio-organic chemistry.     

Mass spectra of polymeric thioformaldehydes (CH2S)3, (CH2S)4, (CH2S)5 and (CH2S)x

The mass spectral fragmentations of various thioformaldehydes, 1,3,5-trithiacyclohexane, 1,3,5,7-tetrathiacyclooctane, 1,3,5,7,9-pentathiacyclodecane and a polymeric form (CH₂S)_x have been examined. The principal features of the spectra are reported. The fragmentation occurred by fracture of the ring in the cyclic compounds with or without rearrangement.     

Asymmetric conjugate reductions with samarium diiodide: asymmetric synthesis of (2S,3R)- and (2S,3S)-[2-2H,3-2H]-leucine-(S)-phenylalanine dipeptides and (2S,3R)-[2-(2)H,3-2H]-phenylalanine methyl ester

The highly diastereoselective samarium diiodide and D(2)O-promoted conjugate reduction of homochiral (E)- and (Z)-benzylidene and isobutylidene diketopiperazines (E)-5,7 and (Z)-6,8 has been demonstrated. This methodology allows the asymmetric synthesis of methyl (2S,3R)-dideuteriophenylalanine 27 in > or = 95% de and >98% ee, and (2S,3R)- or (2S,3S)-dideuterioleucine-(S)-phenylalanine dipeptides 37 and 38 in moderate de, 66% and 74% respectively. A mechanism is proposed to account for this process.     

Enantioselective synthesis of (2R,3R)- and (2S,3S)-2- [(3-chlorophenyl)-(2-methoxyphenoxy)methyl]morpholine

The enantioselective synthesis of the (R,R)- and (S,S)-enantiomers of 1 from commercially available 3-chlorocinnamic acid is reported. The Sharpless asymmetric epoxidation was used to establish the stereocenters in the synthesis of both enantiomers of 1.     

(2R，3R)-和(2S，3S)-2-(4-羟基-3-甲氧基)-3-羟甲基-1，4-苯并二氧六环-6-醛的对映选择性合成

1,4-苯并二氧六环木脂素类天然产物多数具有增加胆碱乙酰化酶和抗肝毒等活性 ,其活性主要源于 1 ,4-苯并二氧六环官能团 [1] . 1 ,4-苯并二氧六环木脂素的消旋全合成已有报道 [2 ] ,但其不对称合成还是空白[3] .我们发展了一条对映选择性合成 1 ,4-苯并二氧六环木脂素的简捷有效的路线 .基于前面的工作 [4 ] ,我们发现 1 ,4-苯并二氧六环醛类衍生物是合成此类天然产物的关键中间体 ,选择 2 - (4-羟基- 3-甲氧基 ) - 3-羟甲基 - 1 ,4-苯并二氧六环 - 6-醛 (1 )作为目标分子 ,其合成路线如下 :Reagents and conditions:( ) Me OH,H2 SO4,9…     

Synthesis of(+)-(2S, 6S)-trans-α-Irone and of(-)-(2S, 6S)-trans-γ-Irone

A 3:1 mixture of (+)-(2S, 6S)-trans-α-irone ((+)-1) and (?)-(2S, 6S)-trans-γ-irone (?)-2) has been synthesized with ca. 70% e. e. by the ene reaction of (?)-(S)-3 and but-3-yn-2-one.     

Stereoselective synthesis of (2S,3S)-3-hydroxy-2-phenylpiperidine from d-mannitol

A novel stereoselective synthesis of N-Boc-(2S,3S)-3-hydroxy-2-phenylpiperidine was achieved from d-mannitol involving the highly stereoselective addition of phenyl Grignard to an allyl imine (de >98%) and ring-closing metathesis (RCM) in the key steps.     

Stereoselective synthesis of conformationally constrained (2S,3S)-3-hydroxyornithine

A convenient and efficient route is described for the highly stereoselective synthesis of δ-amino protected and conformationally restricted (2S,3S)-3-hydroxyornithine through the N-benzylnitrone adduct to the α,β-unsaturated bicyclic lactam 2 derived from (S)-pyroglutaminol.     

Synthesis of (2S,3S)-[3-(2)H1]-4-methyleneglutamic acid and (2S,3R)-[2,3-(2)H2]-4-methyleneglutamic acid

(2S,3S)-[3-(2)H1]-4-Methyleneglutamic acid 1a and (2S,3R)-[2,3-(2)H2]-4-methyleneglutamic acid 1b have been synthesised for use in biosynthetic and metabolic studies.