163799-44-8

Upstream product

• 90-63-1 (RS)-1-hydroxy-1-phenylpropan-2-one 
• 18162-48-6 tert-butyldimethylsilyl chloride 
• 83205-07-6 1-tert-butyldimethylsilyloxy-1-phenyl-2-methylprop-2-ene 
• 100-52-7 benzaldehyde 
• 164853-29-6 (±)-methyl 2-{[(tert-butyldimethylsilyl)oxy](phenyl)methyl}prop-2-enoate 
• 18020-59-2 methyl 3-hydroxy-2-methylidene-3-phenylpropionate 
• 1038432-29-9 (+/-)-2-{[(tert-butyldimethylsilyl)oxy](phenyl)methyl}prop-2-enoic acid 

Downstream Products

• 182196-52-7 [1-(tert-Butyl-dimethyl-silanyloxy)-2-trimethylsilanyloxy-allyl]-benzene 
• 90-63-1 (RS)-1-hydroxy-1-phenylpropan-2-one 
• 189072-85-3 (3R,4S)-3-[(1R)-1-tert-butyldimethylsiloxyethyl]-4-(3-tert-butyldimethylsiloxy-3-phenyl-2-oxopropyl)azetidin-2-one 
• 1855-09-0 1-phenyl-1,2-propandiol 

Relevant academic research and scientific papers

Sequential Reduction of Nitroalkanes Mediated by CS2 and Amidine/Guanidine Bases: A Controllable Nef Reaction

In this letter, we describe a mild, functional group-tolerant reductive Nef reaction that utilizes CS2 and an amidine or guanidine base to sequentially cleave N-O bonds. These conditions transform secondary nitroalkanes to ketones via an isolable oxime with minimal erosion at labile stereogenic carbons, show excellent compatibility with groups sensitive to oxidizing or reducing conditions, display good scalability, and are well-suited for generating useful 3-pyrrolidinone motifs from readily accessible 1,3-dipolar cycloaddition products.

Hyphenating the curtius rearrangement with morita-baylis-hillman adducts: Synthesis of biologically active acyloins and vicinal aminoalcohols

Using Morita-Baylis-Hillman adducts as substrates, the Curtius rearrangement was performed in a sequence that allowed the synthesis of several hydroxy-ketones (acyloins) with great structural diversity and in good overall yields. These acyloins in turn were easily transformed into 1,2-anti aminoalcohols through a highly diastereoselective reductive amination step. The synthetic utility of these approaches was exemplified by performing the syntheses of (±)-bupropion, a drug used to treat the abstinence syndrome of smoker and (±)-spisulosine, a potent anti-tumoral compound originally isolated form a marine source.

Acyloins from Morita-Baylis-Hillman adducts: an alternative approach to the racemic total synthesis of bupropion

In this Letter, we describe an easy and straightforward strategy for the preparation of acyloins (α-hydroxyketones) from Morita-Baylis-Hillman adducts, based on a Curtius rearrangement. Different acyloins were obtained with good overall yield (>40% for three steps). To exemplify the synthetic usefulness of this strategy, total synthesis of (±)-bupropion, a dopamine, and nor-epinefrine reuptake inhibitor has been accomplished in eight steps with an overall yield of 25%.

A convenient and versatile method for the preparation of α-hydroxymethyl ketone derivatives from the corresponding allyl silyl ethers or allyl carboxylates

The ozonolysis of 1-substituted allyl silyl ethers or 1-substituted allyl carboxylates followed by treatment with bases gave the corresponding α-silyloxymethyl- or α-acyloxymethyl-ketones in good yields. It is proposed to proceed via the corresponding α-silyloxy- or α-acyloxyaldehydes intermediates followed by 1,4-group migration. The results of theoretical calculations are applicable to explain the experimental results.

Reversal of the facial diastereoselectivity in the Paterno-Buchi reaction of silyl enol ethers carrying a chiral substituent in α-position

The facial diastereoselectivity in the Paterno-Buchi reaction of benzaldehyde and silyl enol ethers 1 which bear a chiral substituent R* in α-position has been studied. Since the regioselectivity and the simple diastereoselectivity of the photocycloaddition is very good only two diastereoisomers are obtained whose ratio reflects the facial diastereoselectivity. With the silyloxy substituted substrates 1a-1c the selectivity is low (d.r. = 60/40). The benzyloxy substituted silyl enol ether 1d (R* = CHOBni-Pr), however, exhibits already a significant degree of diastereofacial selection and yields preferentially the oxetane 2d (d.r. = 67/33). If the benzyloxy substituent in the substrate is replaced by a chlorine atom (R* = CHCli-Pr) the direction of the facial diastereoselectivity is reverted. Thus, the reaction of silyl enol ether 1e with benzaldehyde gives preferentially oxetane 3e (d.r. = 85/115).