126178-08-3

Upstream product

• 74181-34-3 2,2,-dimethyl-1,3-dioxan-5-one 
• 72748-99-3 (R)-1-Amino-2-(methoxymethyl)pyrrolidine 

Downstream Products

• 902454-76-6 C₃₉H₆₈N₂O₇Si 
• 902454-77-7 C₇₁H₁₂₀O₁₃Si₃ 
• 928113-00-2 acetic acid 4-acetoxy-5-(2,2-dimethyl-5-methylene-[1,3]dioxan-4-yl)-1-[5-(1-hydroxy-allyl)-2,6,6-trimethyl-cyclohex-1-enyl]-pent-2-ynyl ester 
• 928113-08-0 acetic acid 1-{5-[1-(tert-butyl-diphenyl-silanyloxy)-allyl]-2,6,6-trimethyl-cyclohex-1-enyl}-5-(2,2-dimethyl-5-methylene-[1,3]dioxan-4-yl)-4-hydroxy-pent-2-ynyl ester 
• 928112-98-5 acetic acid 1-{5-[1-(tert-butyl-diphenyl-silanyloxy)-allyl]-2,6,6-trimethyl-cyclohex-1-enyl}-5-(2,2-dimethyl-5-methylene-[1,3]dioxan-4-yl)-4-hydroxy-pent-2-ynyl ester 
• 928112-99-6 acetic acid 4-acetoxy-1-{5-[1-(tert-butyl-diphenyl-silanyloxy)-allyl]-2,6,6-trimethyl-cyclohex-1-enyl}-5-(2,2-dimethyl-5-methylene-[1,3]dioxan-4-yl)-pent-2-ynyl ester 
• 554416-43-2 4-[4-(tert-butyl-dimethyl-silanyloxymethyl)-5-(tert-butyl-diphenyl-silanyloxy)-3-methyl-pent-3-enyl]-2,2-dimethyl-[1,3]dioxane-5-carbonitrile 

Relevant academic research and scientific papers

Asymmetric synthesis of synargentolide A and its 3-epimer using the RAMP-hydrazone methodology

Synargentolide A was synthesized in 11 steps starting from the commercially available 2,2-dimethyl-1,3-dioxan-5-one, employing the SAMP/RAMP-methodology via an α,α′-bis-alkylation to generate the first two stereogenic centers with virtually complete asymmetric induction (de, ee >99%). After the asymmetric synthesis of the triol fragment of the molecule, the δ-lactone moiety was constructed using an asymmetric allylation, esterification, and ring-closing metathesis sequence. Georg Thieme Verlag Stuttgart - New York.

Asymmetric synthesis of (+)-altholactone: A styryllactone isolated from various goniothalamus species

The asymmetric total synthesis of (+)-altholactone (1), a member of the styryllactone family of natural products displaying cytotoxic and antitumor activities, is described. Key steps include a RAMP-hydrazone a-alkylation (RAMP = (R)-1-amino-2-methoxymethylpyrrolidine) of 2,2-dimethyl-1,3-dioxan-5-one, a boron-mediated aldol reaction, a six- to five-membered ring acetonide shuffling, an oxidative 1,5-diol to δ-lactone conversion and a stereoselective ring-closure to generate the annulated tetrahydrofuran moiety with inversion of configuration.

Stereoselective synthesis of advanced intermediates en route to Taxuspine U and X: a study of macrocyclization via ring closing metathesis to highly constrained twelve-membered rings

The stereoselective synthesis of an advanced intermediate of Taxuspine U and X has been accomplished using a ring closing metathesis strategy. The feasibility of ring closing metathesis in synthesizing highly constrained and functionalized macrocycles has been demonstrated provided the appropriate substrate structure and substitution pattern are chosen.

Synthesis of iso-epoxy-amphidinolide N and des-epoxy-caribenolide i structures. Initial forays

Two strategies for the projected total synthesis of the phenomenally potent antitumour macrolides amphidinolide N (1) and caribenolide I (2) are described. The title compounds are introduced as challenging and unique targets for chemical synthesis, and their retrosynthetic analysis is presented. The synthesis of the four defined key building blocks (10, 39, 67 and 72), required for the construction of amphidinolide N (1), in their enantiomerically pure forms, is described, followed by the coupling of 10, 39 and 72 through hydrazone alkylation processes to generate the complete C6-C29 carbon framework of the target compound (1). Fusion of the remaining C1-C5 sector (72) onto the molecule by metathesis-based methods was unsuccessful, resulting in the adoption of a second-generation strategy which called for the employment of one of the array of palladium-catalysed cross-coupling reactions to generate the C5-C6 carbon-carbon bond. Vinyl bromide 125, representing the C6-C29 skeleton of caribenolide I (2), was prepared through the sequential alkylation of hydrazone 10 with bromide 116 and iodide 55, but failed to engage in the appropriate cross-coupling reaction with a variety of C1-C4 partners. Despite these setbacks, the information gleaned from these endeavours was to prove invaluable in laying the foundation for the eventual successful approach to the macrocyclic structures of amphidinolide N (1) and caribenolide I (2). The Royal Society of Chemistry 2006.

Asymmetric synthesis of protected 2-keto-1,3-diol and 1,2,3-triol building blocks bearing a quaternary stereogenic center

The asymmetric synthesis of protected 2-keto-1,3-diols 5 and 1,2,3-triols 6 bearing a quaternary stereogenic center starting from 2,2-dimethyl-1,3-dioxan-5-one (1) is described. The stereogenic centers are generated by sequential α-alkylation of 1 using the SAMP/RAMP hydrazone method and stereoselective reduction of ketones 5 with L-selectride. The products are obtained in good yields and high diastereomeric and enantiomeric excesses.

Enantioselective Alkylation of 2,2-Dimethyl-1,3-dioxan-5-one Using the SAMP-/RAMP-Hydrazone Method

The lithiated SAMP-hydrazone (S)-3 is used as a chiral 1,3-dihydroxyacetone-enolate equivalent C in overall enantioselective α-alkylations leading to 4-alkyl-2,2-dimethyl-1,3-dioxan-5-ones (S)-5a-i in good overall chemical yields and of high enantiomeric purity (ee = 88 - >/= 93percent.