84823-48-3

Upstream product

• 504-61-0 (E)-but-2-enol 
• 4088-60-2 cis-2-buten-1-ol 
• 267236-28-2 (2S,3R)-2,3-epoxy-1-[(4-methoxyphenyl)diphenylmethoxy]butane 
• 105393-76-8 (2R,3R)-2-bromobutane-1,3-diol 
• 10133-06-9 Methyl (2R,3R)-2,3-epoxybutanoate 

Downstream Products

• 119089-56-4 (2S,3R)-2,3-epoxy-1-butanol (R)-α-methoxy-α-(trifluoromethyl)phenylacetate 
• 1192872-98-2 C₁₁H₁₄O₂ 
• 1453203-57-0 (2S,3R)-2-((4-methoxybenzyloxy)methyl)-3-methyloxirane 
• 72229-17-5 (2S,3R)-2-[(benzyloxy)methyl]-3-methyloxirane 
• 267236-28-2 (2S,3R)-2,3-epoxy-1-[(4-methoxyphenyl)diphenylmethoxy]butane 

Relevant academic research and scientific papers

Total Synthesis of Mycinolide IV and Path-Scouting for Aldgamycin N

Proof-of-concept is provided that a large estate of 16-membered macrolide antibiotics can be reached by a “unified” approach. The key building block was formed on scale by an asymmetric vinylogous Mukaiyama aldol reaction; its alkene terminus was then converted either into the corresponding methyl ketone by Wacker oxidation or into a chain-extended aldehyde by catalyst-controlled branch-selective asymmetric hydroformylation. These transformations ultimately opened access to two structurally distinct series of macrolide targets. Notable late-stage maneuvers comprise a rare example of a ruthenium-catalyzed redox isomerization of an 1,3-enyne-5-ol into a 1,3-diene-5-one derivative, as well as the elaboration of a tertiary propargylic alcohol into an acyloin by trans-hydrostannation/Chan-Lam-type coupling. Moreover, this case study illustrates the underutilized possibility of forging complex macrolactone rings by transesterification under essentially neutral conditions.

Total Synthesis of the Marine Macrolide Amphidinolide F

A new and efficient convergent approach toward the synthesis of amphidinolide F is described through the assembly of three fragments. The two trans-tetrahydrofurans were built by a diastereoselective C-glycosylation with titanium enolate of bulky N-acetyloxazolidinethiones. The side chain was inserted by a Liebeskind-Srogl cross-coupling reaction. A sulfone condensation/desulfonylation sequence, a Stille cross-coupling, and a macrolactonization were applied to connect the fragments.

Total Synthesis of Putative Chagosensine

The marine macrolide chagosensine is the only natural product known to date that embodies a Z,Z-configured chloro-1,3-diene unit. This distinguishing substructure was prepared by a sequence of palladium-catalyzed 1,2-distannation of an alkyne precursor, regioselective Stille cross-coupling at the terminus of the resulting bisstannyl alkene with an elaborated alkenyl iodide, followed by chloro-destannation of the remaining internal site. The preparation of the required substrates centered on cobalt-catalyzed oxidative cyclization reactions of hydroxylated olefin precursors, which allowed the 2,5-trans-disubstituted tetrahydrofuran rings, embedded into each building block, to be formed with excellent selectivity. The highly strained macrolactone could ultimately be closed under forcing Yamaguchi conditions. Comparison of the spectral data of the synthetic sample with those of authentic chagosensine methyl ester confirmed that the structure of this intriguing compound has been mis-assigned by the isolation team.

Studies for the total synthesis of amphidinolide P

A convergent, enantiocontrolled total synthesis of the 15-membered macrolide, amphidinolide P, is described. The synthesis utilizes three nonracemic components for an efficient assembly of the macrolactone in 12 steps via the longest linear pathway. Key developments include studies of the Hosomi-Sakurai reaction for the formation of the C6-C7 bond, a "ligandless" palladium-mediated Stille cross-coupling of the vinylic stannane 4 and the alkenyl bromide 5 to produce a highly functionalized dienol, and a thermally induced, intramolecular lactonization via the late-stage formation of an intermediate α-acylketene.

Gram scale synthesis of the C(1)-C(9) fragment of amphidinolide C

An allylic cis-epoxide prepared by Sharpless asymmetric epoxidation was transformed in nine steps and 41% overall yield to the cyclization precursor 4 via a key one carbon homologation. Cobalt-catalyzed aerobic oxidative cyclization of 4 gave the trans-TH

Enantioselective epoxidation of nonconjugated cis-olefins by chiral dioxirane

A variety of nonconjugated cis-olefins has been enantioselectively epoxidized with chiral ketones 2, and up to 92% ee has been obtained. The two prochiral faces of an olefin are likely stereodifferentiated by the relative hydrophobicity of the olefin substituents and/or allylic oxygen functionality.

Development and application of versatile bis-hydroxamic acids for catalytic asymmetric oxidation

In this article, we describe the development and preliminary results of our new designed C2-symmetric bis-hydroxamic acid (BHA) ligands and the application of the new ligands for vanadium-catalyzed asymmetric epoxidation of allylic alcohols as well as homoallylic alcohols. From this success we demonstrate the versatile nature of BHA in the molybdenum catalyzed asymmetric oxidation of unfunctionalized olefins and sulfides.

Enantioselective epoxidation of allylic alcohols by a chiral complex of vanadium: An effective controller system and a rational mechanistic model

(Chemical Equation Presented) Bishydroxamic acid derivatives are used as ligands for a vanadium catalyst in the preparation of epoxy alcohols (see scheme). The methodology uses aqueous tert-butyl hydroperoxide (TBHP) as an achiral oxidant, low catalyst loading, low reaction temperatures (0°C to room temperature), and simple workup procedures. The reaction is applied to the kinetic resolution of a secondary allylic alcohol and the preparation of small epoxy alcohols. R1, R2, R3: alkyl, aryl, H.

Synthesis of 3-fluoro azetidinone by electrophilic fluorination

An easy access to the 3-fluoroazetidinone 4a based on electrophilic fluorination, is reported. The fluorination of the β-lactam 7 with Differding's N-fluorosulfonimide proceeds stereoselectively, under mild conditions and in good yield.

π-Allyl palladium ring closure strategy for the synthesis of a 1β-methylcarbapenem intermediate

A new ring closure by π-allyl palladium methodology is utilized in the synthesis of a 1-β-methyl carbapenem intermediate from 2-acetoxy azetidinone in six steps (40% yield).