5849-19-4

Upstream product

• 505-23-7 1,3 dithiane 
• 100-52-7 benzaldehyde 
• 13411-42-2 2-(trimethylsilyl)-1,3-dithiane 
• 78350-65-9 (S(CH₂)3S)CHTi(OCH(CH₃)2)3 
• 36049-90-8 2-lithio-1,3-dithiane 

Downstream Products

• 60973-46-8 2-phenyl-6,7-dihydro-5H-1,4-dithiepine 
• 612-94-2 2-phenylnaphthalene 
• 100-52-7 benzaldehyde 
• 1231151-32-8 1-phenyl-2-[(3-sulfanylpropyl)sulfanyl]ethan-1-one 
• 93-58-3 benzoic acid methyl ester 

Relevant academic research and scientific papers

Bu4N+ alkoxide-initiated/autocatalytic addition reactions with organotrimethylsilanes

The use of Me3SiO-/Bu4N+ as a general activator of organotrimethylsilanes for addition reactions has been established. The broad scope of the method offers trimethylsilanes (including acetate, allyl, propargyl, benzyl, dithiane, heteroaryl, and aryl derivatives) as bench-stable organometallics that can be readily utilized as carbanion equivalents for synthesis. Reactions are achieved at rt without the requirement of specialized precautions that are commonplace for other organometallics.

Aniline mediated oxidative C-C bond cleavage of α-alkoxy aldehydes in air and a model reaction for the synthesis of α-(d)-amino acid derivatives

A metal-free and 4-methyl aniline mediated method for the oxidative C-C bond cleavage has been developed. The reaction proceeds in air using molecular oxygen as the oxidant, affording one-carbon shortened esters in moderate to good yields within a short time. Moreover, it provides a model reaction for the highly enantioselective synthesis of (d)-serine esters by combining with a l-proline catalyzed Mannich reaction.

Acid-induced rearrangement reactions of -hydroxy-1,3-dithianes

Secondary benzylic or aliphatic -hydroxydithianes 1a-c rearrange to -thioketones when treated with acid. Related tertiary alcohols 1d-g eliminate to dithioketene ketals (e.g., 2d), which are ring-opened to thiols in some cases (1e, 1f). Allylic -hydroxydi

P(i-PrNCH2CH2)3N: an efficient catalyst for TMS-1,3-dithiane addition to aldehydes

Herein we report the use of commercially available P(i-PrNCH2CH2)3N (1a) as an efficient catalyst for 2-trimethylsilyl-1,3-dithiane (TMS-dithiane) addition to aldehydes at room temperature. The catalyst loading required fo

Lewis base catalyzed 1,3-dithiane addition to carbonyl compounds using 2-trimethylsilyl-1,3-dithiane

1,3-Dithiane addition to various aldehydes and ketones using 2-trimethylsilyl-1,3-dithiane in the presence of a catalytic amount of a Lewis base such as tetrabutylammonium phenoxide (PhONn-Bu4) proceeds smoothly to afford the corresponding α-hy

Remote substituent effect favoring the formation of syn-adducts in the chelation controlled radical reactions of γ-benzyloxy-α-methylenecarboxylic acid esters

The chelation controlled radical reactions of ethyl γ-benzyloxy-α-methylenecarboxylates bearing a bulky γ-substituent, such as CHMe2, CHPh2, c-C6H11 and CH(Ph)OTBDMS, with alkyl iodides gave the syn-adducts with high diastereoselectivities. However, the diastereoselectivity for the substrates bearing a γ-substituent CH(i-Pr)OTBDMS depended critically on the configuration of the substituent; the substrate bearing the OTBDMS group anti to the γ-benzyloxy group showed poor diastereoselectivity, but its diastereomer gave syn-adduct exclusively. The high syn-selectivitiy is referred to the H-atom transfer to the outside face of radical center in the sharply folded seven-membered chelate intermediate bearing the ethoxy group with Z-geometry. The corner flapping of the radical center atom of the global minimum energy conformer generates a local minimum conformer and the H-atom transfer to the outside face of the radical center of the newly formed structure gives the anti-adduct. The poor diastereoselectivity is due to the very small energy difference between the two conformers and consequently both the syn- and anti-adducts are yielded in nearly equal amounts.

Electronic control of product formation in the rearrangement of 1,3-dithian-2-yl-arylmethanols

1,3-Dithian-2-yl-phenylmethanols undergo efficient rearrangement to afford 2-phenyl-6,7-dihydro-5H-1,4-dithiepines. The reactions were found to show remarkable variation in products formation that is dictated by the substituents on the aryl ring.

A convenient high yield synthesis of functional methacrylates via dethioacetalization. Synthesis of methacrylate S,S-acetal derivatives as intermediates

We describe a selective and efficient synthesis of a whole new class of functional methacrylates starting from S,S-acetals. Carbonyl compounds were regenerated from corresponding S,S-acetaIs using mercury (II) salts. According to this method, methacrylic

An efficient photo-SET-induced cleavage of dithiane-carbonyl adducts and its relevance to the development of photoremovable protecting groups for ketones and aldehydes

Irradiation of dithiane-aldehyde/ketone adducts in the presence of benzophenone leads to C-C bond cleavage regenerating the carbonyl compounds. It is established that the mechanism of this reaction involves photochemically induced single electron transfer from the dithiane moiety to the excited molecule of ET-photosensitizer, accompanied by mesolytic C-C cleavage in the generated cation-radical, which is assisted by the anion- radical of benzophenone. This mechanism is confirmed by a Hammett plot study of the cleavage in the dithiane adducts of substituted aromatic aldehydes and a deuterium kinetic isotope effect study. Ab initio computations at UHF/6- 31G* and MP2/6-31G* levels of theory in conjunction with self-consistent reaction field (self-consistent isodensity-polarized continuum model), to account for the solvent effect, also support the experimental findings. The reaction is most efficient for protection of aromatic aldehydes and ketones and aliphatic ketones, and is a novel method for protecting carbonyl functionalities with a photoremovable group.

Ti-TADDOLate-Catalyzed, Highly Enantioselective Addition of Alkyl- and Aryl-Titanium Derivatives to Aldehydes

Toluene-ether or toluene-hexane solutions of aryl and alkyl triisopropoxy titanium reagents (free of Li, Mg, or Zn salts) are prepared from the corresponding Li or Grignard reagents and ClTi(OiPr)3, with careful removal of salts (centrifugation of LiCl or of dioxane*MgX2, and addition of 12-crown-4).The solutions of the organotitanium compounds are combined with one equiv. of an aldehyde and 0.2 equiv. of (R,R)-diisopropoxy-(α,α,α',α'-tetraphenyl-2,2-dimethyl-1,3-dioxolane-4,5-dimethanolato) titanium (Ti-TADDOLate 3) at dry-ice temperature.Warming up to room temperature leads to nucleophilic addition to the (Si)-face of the aldehydes with enantioselectivities as high as 99.5 : 0.5 (products 4-33 in Scheme 4).Functional groups or protecting groups and branching in the Ti-R group and in the aldehyde must be remote from the reacting centers.Aryl groups can be added to aldehydes by this method. - In contrast to all the enantioselective R2Zn additions to aldehydes, in which only one R-group is actually transferred, a twice as economic use is made of the originally employed R-metal reagent in the method described here. - A procedure for multigram preparation of the spiro-Ti-TADDOLate (2) employed for the in situ generation of catalyst (3) is described, and details of the determination of enantiomer ratios (er) by GC and NMR methods are given (Tab. 2, 3).The mechanistic interpretation of Ti-TADDOLate-mediated nucleophilic additions as derived previously (ref.4c) is also compatible with this monometallic variant of the method.