664997-48-2

Upstream product

• 29264-40-2 5-pentenylbenzoate 
• 89527-11-7 3-(oxiran-2-yl)propyl benzoate 
• 664997-56-2 Benzoic acid (R)-3-oxiranyl-propyl ester 

Downstream Products

• 664997-54-0 C₄₂H₆₈O₄Si₂ 
• 664997-58-4 C₄₂H₆₈O₄Si₂ 
• 664997-53-9 (1S,3R,4S)-3-[(E)-(R)-4-Benzyloxy-1-(tert-butyl-dimethyl-silanyloxy)-but-2-enyl]-4-((E)-(S)-6-benzyloxy-hept-1-enyl)-cyclopentanol 
• 664997-57-3 (1R,3R,4S)-3-[(E)-(R)-4-Benzyloxy-1-(tert-butyl-dimethyl-silanyloxy)-but-2-enyl]-4-((E)-(S)-6-benzyloxy-hept-1-enyl)-cyclopentanol 
• 664997-52-8 (3R,4S)-3-[(E)-(R)-4-Benzyloxy-1-(tert-butyl-dimethyl-silanyloxy)-but-2-enyl]-4-((E)-(S)-6-benzyloxy-hept-1-enyl)-cyclopentanone 
• 664997-50-6 C₁₄H₂₁BO₃ 
• 664997-51-7 (E)-(S)-6-benzyloxy-hept-1-ene 
• 664997-49-3 ((S)-1-Methyl-hex-5-ynyloxymethyl)-benzene 
• 231291-69-3 (S)-4-Benzyloxy-pentan-1-ol 
• 20350-15-6 (+)-brefeldin A 

Relevant academic research and scientific papers

Enantioselective total synthesis of (+)-brefeldin A and 7-epi-brefeldin A

A convergent enantioselective route to brefeldin A (BFA) and 7-epi-BFA was developed. The key C-4/C-5 chiral centers were established by using chiral auxiliary induced intermolecular asymmetric aldolization in the presence of TiCl4 and TMEDA. The results with the thiazolidinethione/TiCl 4 mediated intermolecular asymmetric aldolization added some new information about the scope and limitations to the existing knowledge of that type of reactions (which so far was essentially limited to the reactions with N-propionyl thiazolidinethiones). During the course a method for protecting the liable aldol hydroxyl groups by using inexpensive TBSCl in DMF with 2, 6-lutidine as the base was developed to replace the otherwise unavoidable TBSOTf procedure. Due to the excessive steric hindrance, removal of the auxiliary was much more difficult than most literature cases. Cleavage of the oxazolidinone by reduction was almost impossible. The thiazolidinethione auxiliary was relatively easier to remove. However, several reactions reported for facile removal of thiazolidinethione auxiliaries in the literature still failed. Reductive removal of the thiazolidinethione auxiliary was most effectively realized with LiBH4 in diethyl ether in the presence of 1 equiv of MeOH (a modification of a literature procedure for removal of oxazolidinone auxiliaries in less hindered substrates). Apart from the auxiliary removal, oxidation of the alcohol into aldehyde and the deprotection of the dithiolane protecting group were also rather difficult in the present context. A range of methods were screened before final solutions were found. The five-membered ring was constructed by employing an intramolecular Mukaiyama reaction after many attempts with the intramolecular aldolization under a variety of conditions failed. The rate of elimination of the alkoxyl to form the α,β-double bond of the key intermediate cyclopentenone 49 with DBU was highly solvent dependent (very sluggish in CH2Cl2 but rather fast in MeOH). Introduction of the lower chain (which was synthesized by using a Jacobsen KHR to establish the C-15 chirality) was achieved through a Michael addition similar to the precedents in the literature. It has not been noticed before that the yield of this Michael reaction could be dramatically raised by using 3 equiv of the copper-lithium reagent 55. Reduction of the C-7 carbonyl was apparently more difficult than similar cases in the literature. After examination of many reagents under various conditions, it was found that the best reagent for yielding the α-isomer was (S)-2-methyl-CBS-borolidine/BH3 and that for the β-isomer was L-Selectride. The α- and β-isomers were then further elaborated into (+)-brefeldin A and 7-epi-BFA, respectively. An unexpected yet very interesting solubility difference between BFA and 7-epi-BFA was also observed.

An aldol approach to the total synthesis of (+)-brefeldin a

A convergent selective route to (+)-brefeldin A (BFA) and 7-epi-BFA was developed, with the crucial C-4/C-5 stereogenic centers were established using Crimmins asymmetric aldolization.

Asymmetric Hydrosilylation of 1-Alkenes Catalyzed by Palladium-MOP

Asymmetric hydrosilylation of simple terminal alkenes (RCH=CH2) with trichlorosilane at 40 deg C in the presence of 1*10-3 or 1*10-4 molar amounts of palladium catalyst prepared in situ from 3-C3H5)>2 and (S)-2-diphenylphosphino-2'-methoxy-1,1'-binaphthyl ((S)-MeO-MOP) proceeded with unusual regioselectivity and with high enantioselectivity to give high yields of 2-(trichlorosilyl)alkanes together with a minor amount of 1-(trichlorosilyl)alkanes.Optically active alcohols, RCH(OH)CH3, were obtained by oxidation of the carbon-silicon bond.Regioselectivities for forming 2-silylalkanes over 1-silylalkanes and enantiomeric purities of alcohols are as follows: R=n-C4H9: 89/11, 94percent ee (R).R=n-C6H13: 93/7, 95percent ee (R).R=n-C10H21: 94/6, 95percentee (R).R=PhCH2CH2: 81/19, 97percentee (S).R=PhCH2CH2CH2: 80/20, 92percent ee (R).R=cyclo-C6H11: 66/34, 96percent ee (R).A similar hydrosilylation of 1-alkenes, 4-pentenyl benzoate and 1,5-heptadiene gave corresponding 2-alkanols of 90percent ee and 87percent ee, respectively, the ester carbonyl and the internal double bond remaining intact.