88157-27-1

Upstream product

• 18162-48-6 tert-butyldimethylsilyl chloride 
• 603-35-0 triphenylphosphine 
• 627-30-5 1-chloro-3-hydroxypropane 
• 78878-05-4 1-iodo-3-(tert-butyldimethylsilyloxy)propane 
• 89031-82-3 1-(t-Butyldimethylsilyloxy)-3-chloro-propane 
• 73842-99-6 3-tert-butyldimethylsilyloxy-1-propanol 

Downstream Products

• 161984-56-1 (2S,3R,4aS,6R,7S,8aR)-3-Benzyloxy-2-(2-benzyloxy-ethyl)-7-(tert-butyl-dimethyl-silanyloxy)-6-[(Z)-4-(tert-butyl-dimethyl-silanyloxy)-but-1-enyl]-2,4a,6-trimethyl-octahydro-pyrano[3,2-b]pyran 
• 714966-74-2 (E)-3-{2-[(Z)-6-(tert-Butyl-dimethyl-silanyloxy)-hex-3-enyl]-4-methoxy-phenyl}-acrylic acid ethyl ester 
• 714966-82-2 (E)-3-{2-[(Z)-6-(tert-Butyl-dimethyl-silanyloxy)-hex-3-enyl]-4-methoxy-phenyl}-prop-2-en-1-ol 
• 1000992-99-3 C₁₉H₃₂O₃Si 
• 161984-57-2 (2S,3R,4aS,6R,7S,8aR)-3-Benzyloxy-2-(2-benzyloxy-ethyl)-7-(tert-butyl-dimethyl-silanyloxy)-6-[4-(tert-butyl-dimethyl-silanyloxy)-butyl]-2,4a,6-trimethyl-octahydro-pyrano[3,2-b]pyran 
• 131318-58-6 [3-(tert-butyl-dimethyl-silanyloxy)-propylidene]-triphenyl-λ⁵-phosphane 

Relevant academic research and scientific papers

Use of the 2-Pyridinesulfonyloxy Leaving Group for the Fast Copper-Catalyzed Coupling Reaction at Secondary Alkyl Carbons with Grignard Reagents

Investigation of the copper-catalyzed coupling reaction of 2-pyridinesulfonates with Grignard reagents revealed that reactions with catalytic Cu(OTf)2 were completed in 40 min. The results differed from those of the previous CuI-catalyzed reactions of tosylates in the presence of additives (LiOMe and TMEDA) for 12-24 h. It was shown that the preferred coordination of the leaving group to the reagents accelerated the reaction. Successful reagents were MeMgCl and other RMgX. Complete inversion was established.

Synthesis of 1,3-Cycloalkadienes from Cycloalkenes: Unprecedented Reactivity of Oxoammonium Salts

Few methods allow for the direct conversion of cycloalkenes into cycloalkadienes with high chemo- and regioselectivity. Herein, we report a convenient one-pot process for this transformation that involves the unprecedented N-preferential group transfer of N-oxoammonium salts to cycloalkenes, followed by Cope elimination, to afford cycloalkadienes at room temperature and pressure.

Asymmetric total synthesis of caribenol A via an intramolecular diels-alder reaction

A total synthesis of the caribenol A (1), a novel natural product with an intriguing tetracyclic framework, has been achieved. The synthesis features an intramolecular Diels-Alder (IMDA) reaction for the facile construction of the tricyclic [5-7-6] skelet

Total synthesis of the calphostins: Application of Fischer carbene complexes and thermodynamic control of atropisomers

The total syntheses of the potent protein kinase C inhibitors calphostins A, B, C, and D as well as a variety of structural analogues are reported. An aminobenzannulation reaction of an enantiopure chromium Fischer carbene complex is utilized to prepare a pentasubstituted naphthylamine. After optimization of side-chain substituents, conversion of the naphthylamine to an o-naphthoquinone was followed by biomimetic oxidative dimerization using trifluoroacetic acid and air yielding a 1:2 P/M mixture of atropisomeric perylenequinones. Thermal equilibration to a 3:1 P:M atropisomeric ratio and separation of the perylenequinones followed by side chain desymmetrization and functionalization led to the total synthesis of enantio- and diastereomerically pure calphostin C in only twelve steps from commercially available starting materials. In addition, calphostins A, B, D, and several structural analogues were prepared to evaluate biological activities.

Samarium(II) iodide-mediated reductive annulations of ketones bearing a distal vinyl epoxide moiety

Samarium(II) iodide in the presence of hexamethylphosphoramide (HMPA) efficiently promotes the intramolecular coupling of ketones with distal epoxy olefins. The reaction appears to proceed by a mechanism wherein a ketyl couples with the unsaturated epoxide. Subsequent fragmentation of the epoxide ring in compounds 1a-k yields carbocycles 2a-k with an allyl alcohol side chain in good yields, and often with high diastereoselectivity. When tetramethylguanidine was used as an additive instead of HMPA, the desired carbocycle was obtained in good yield, but the diastereoselectivity was diminished. A palladium(0)-catalyzed SmI2 reaction provided the expected product in modest yield, but the sense of diastereoselectivity was reversed. In the latter case, a different reaction mechanism may be involved. Thus, formation of an allylsamarium species may be invoked, with nucleophilic carbonyl addition leading to the observed facial selectivity.

Ethanoarachidonic Acids. A New Class of Arachidonic Acid Cascade Modulators. 2. Polyethano Compounds

The total synthesis and preliminary biological data of di- and triethanoarachidonic acids 1-4 are described.