104832-79-3

Upstream product

• 76-86-8 Triphenylsilyl chloride 
• 104755-58-0 (2R,3R)-3-(triphenylsilyl)<2,3-(2)H2>oxiranecarboxaldehyde 
• 104832-80-6 (2S,3S)-3-(triphenylsilyl)<2,3-(2)H2>oxiranemethanol 
• 104755-57-9 (2R,3R)-3-(triphenylsilyl)<2,3-(2)H2>oxiranemethanol 
• 104755-56-8 (E)-3-(Triphenylsilyl)<2,3-(2)H2>prop-2-en-1-ol 
• 51105-91-0 3-(triphenylsilyl)propargyl alcohol 
• 104832-81-7 (2S,3S)-3-(triphenylsilyl)<2,3-(2)H2>oxiranecarboxaldehyde 
• 6229-00-1 triphenylsilylacetylene 
• 136144-91-7 (Z)-dideuterio(triphenylsilyl)ethylene 
• 136144-90-6 (triphenylsilyl)acetylene-d1 
• 59231-24-2 (E)-dideuterio(triphenylsilyl)ethylene 

Downstream Products

• 18666-75-6 β-Deutero-β-triphenylsilylethanol 

Relevant academic research and scientific papers

Synthesis of Cryptochiral (R,R)-2,3-Dideuterooxirane as Stereochemical Reference Compound and Chemical Correlation with D-(+)-Glyceraldehyde

Chirality plays a pivotal role in chemistry and biology, e.g., structure-specific targeting in drug development or the lock-and-key theory of enzyme interactions. Determining absolute configurations of chiral molecules is essential to understanding such mechanisms and to developing chemical processes involving chiral compounds. In particular, this becomes obvious in the understanding of chemical reaction networks in the context of the origins of life. A stereochemical reference compound that can be correlated with sugars, amino acids, etc. is of great interest. Here, we present the synthesis of enantiopure (R,R)-2,3-dideuterooxirane, of which the absolute configuration has been unambiguously determined by foil-induced Coulomb explosion imaging, and the correlation with the configuration of D-(+)-glyceraldehyde.

Coulomb explosion imaged cryptochiral (R,R)-2,3-dideuterooxirane: Unambiguous access to the absolute configuration of (+)-glyceraldehyde

The absolute configuration of (R,R)-2,3-dideuterooxirane, which has been independently determined using Coulomb explosion imaging, has been unambiguously chemically correlated with the stereochemical key reference (+)-glyceraldehyde. This puts the absolute configuration of D(+)-glyceraldehyde on firm experimental grounds. 100% Absolute: The absolute configuration of (R,R)-2,3-dideuterooxirane, which has been independently determined by Coulomb explosion imaging (CEI), has been unambiguously chemically correlated with the stereochemical key reference (+)-glyceraldehyde. This puts the absolute configuration of D(+)-glyceraldehyde on firm experimental grounds (see scheme).

Imaging the absolute configuration of a chiral epoxide in the gas phase

In chemistry and biology, chirality, or handedness, refers to molecules that exist in two spatial configurations that are incongruent mirror images of one another. Almost all biologically active molecules are chiral, and the correct determination of their absolute configuration is essential for the understanding and the development of processes involving chiral molecules. Anomalous x-ray diffraction and vibrational optical activity measurements are broadly used to determine absolute configurations of solid or liquid samples. Determining absolute configurations of chiral molecules in the gas phase is still a formidable challenge. Here we demonstrate the determination of the absolute configuration of isotopically labeled (R,R)-2,3-dideuterooxirane by foil-induced Coulomb explosion imaging of individual molecules. Our technique provides unambiguous and direct access to the absolute configuration of small gas-phase species, including ions and molecular fragments.

Synthesis and stuctures of moderately stable metallaxoetanes: (η5-C5Me5)2(CH 3)TaOCHRCH2= (R=H, C6H5) investigations of their decompositon to olefin and (η5-C5Me5)2 Ta(=O)CH3

Metallaoxetanes Cp*2(CH3)TaOCHRCH2 (Cp* = ((η5-C5Me5); R = H, p-C6H4X; X = H, Cl, CF3, CN, NO2) have been prepared by reaction of Cp*2Ta(=CH2)CH3 with the appropriate aldehyde RCHO, The kinetic products of the 2 + 2 reaction between the benzaldehydes with Cp*2Ta(==CH2)CH3 are O-syn-Cp*2)(CH3)TaCH2)CH(p-C 6)H4X)O, which rearrange in benzene solution at 25°C to the more O-anti-Cp*2(CH3)TaCH2CH(p-C 6H4X)CH2. An X-ray crystal structure determination for O-anti-Cp*2(CH3)TaOCH(C6H 5)CH2 has been carried out (space group P21/c (No. 14) with cell parameters a = 15.677 (10) A?, b = (4) A?, c = 18.315 (18) A?, β= 110.81 (7)°, V= 2550.3 (32) A?3, and Z = 4), a puckered four-membered ring. The distortion from planarity likely arises from close contacts between a pentamethylcyclo-pentadienyl ligand and the phenyl ring. Decomposition of O-anti-Cp*22(CH3)TaOCHRCH2 smoothly at 80°C to afford Cp*2Ta(=O)CH3 and RCH=CH2. The rates for styrene formation depend only slightly on the para substituent and do not correlate with σ orσ=. In a related transformation, Cp*2Ta(=CH2)H reacts with epoxides in THF even at -50°C to yield Cp*2Ta(=O)CH3 and olefin. Significantly, neither Cp*2Ta(=O)CH3 nor O-syn-Cp*2(CH3)-TaCH2CH2O nor O-anti-Cp"2is observed as an intermediate for the deoxygenation of ethylene oxide, and deoxygenation of trans-styrene-d1(CH3) TaOCH2CH2 is observed as an intermediate for the deoxygenation of trans-styrene-d1 oxide, trans-ethylene-d2 oxide with >95% retention of stereochemistry. These result strongly implicate a concerted process and indicate that epoxide deoxygenation and (more importantly) olefin epoxidation with transition-metal derivatives need not involve metallaoxetane intermediates.

Synthesis of (2R,3R)- and (2S,3S)-Oxirane and Application of It to the Synthesis of Chirally Labeled Homoserine

(2R,3R)- and (2S,3S)-oxirane have been synthesized from 2-propynol, the key step being the asymmetric epoxidation of (E)-3-(triphenylsilyl)-2-propenol.To determine the enantiomeric purities of the oxiranes, they were reacted with phenyllithium,

Organosilicon compounds with functional groups proximate to silicon. XVII. Synthetic and mechanistic aspects of the lithiation of α,β-epoxyalkylsilanes and related α-heterosubstituted epoxides

A series of α-heterosubstituted epoxides, , has been found to undergo lithiation in the temperature range of -75 to -115 deg C at the C-H bond of the epoxide.The substituent Z could be Me3Si, Ph3Si, n-Bu3Sn, Ph3Sn, PhSO2, (OEt)2PO and Ph; the groups R and R' were H, Ph and n-C6H13; and the lithiating reagents were n-butyllithium, t-butyllithium and lithium diisopropylamide in donor media of THF or TMEDA.The lithiation occurs with retention of configuration and the resulting lithio-epoxide is unstable above 0 deg C, decomposing in a carbenoid manner.The lithiation is facile except for compounds where Z and R (an alkyl or aryl) are cis-oriented; where Z = R3Sn, lithiation occurs by tin-lithium, rather than hydrogen-lithium, exchange.The lithio-epoxides thereby generated can be quenched with various reagents to yield epoxides where the epoxide H has been replaced by D, Me3Sn, R, RCO and COOH.The utility of this procedure in organic synthesis is emphasized.Finally, the possible explanations for the acidity of such α-heterosubstituted epoxides and for the relative stability of the derived lithio-epoxides are considered and assessed.

Chirally-labelled Oxirane

(R,R)- and (S,S)-oxiranes have been synthesized from prop-2-yn-1-ol, the key step being asymmetric epoxidation of (E)-3-(triphenylsilyl)prop-2-en-1-ol.