130857-02-2

Upstream product

• 63358-54-3 (2S,6S)-6-hydroxymethyl-2-methoxy-5,6-dihydro-2H-pyran 
• 100-39-0 benzyl bromide 
• 10034-09-0 1-methoxy-1,3-butadiene 
• 60656-87-3 benzyloxyacetoaldehyde 
• 646058-48-2 6(S)-carboxymethyl-2-methoxy-5,6-dihydro-2H-pyran 
• 123284-54-8 (2'S)-methoxy-(6'S)-<(2R)bornane-10,2-sultam>-carbonyl-5',6'-dihydro-2H-pyran 
• 199393-63-0 (2S)-1-(benzyloxy)-3-(3-{[(4-methoxybenzyl)oxy]methyl}-5,6-dihydro-1,4-dithiin-2-yl)propan-2-ol 
• 199393-67-4 Acetic acid (S)-1-benzyloxymethyl-2-[3-(4-methoxy-benzyloxymethyl)-5,6-dihydro-[1,4]dithiin-2-yl]-ethyl ester 
• 199393-72-1 Acetic acid (S)-1-benzyloxymethyl-2-(3-formyl-5,6-dihydro-[1,4]dithiin-2-yl)-ethyl ester 
• 2930-05-4 (S)-benzyl glycidyl ether 
• 790667-32-2 (5S,7S)-7-[(benzyloxy)methyl]-5-methoxy-2,3,7,8-tetrahydro-5H-[1,4]dithiino[2,3-c]pyran 
• 22870-42-4 5,6-dihydro-6-(hydroxymethyl)-2-methoxy-2H-pyran 

Downstream Products

• 790667-34-4 methyl 6-O-benzyl-4-deoxy-α-D-lyxo-hexopyranoside 
• 124662-66-4 (6S)-6-[(phenylmethoxy)methyl]-5,6-dihydro-2H-pyran-2-one 

Relevant academic research and scientific papers

Diastereoselective Synthesis of the Lactone Portion of Compactin and Mevinolin

The highly diastereoselective cycloaddition of 1-methoxybuta-1,3-diene (3) to (2R)-N-glyoxyloylbornane-10,2-sultam (2) afforded the adduct (4) which was effectively transformed into (4R,6S)-4-hydroxy-6-hydroxymethyltetrahydro-2-pyrone (1), a key synthon for the lactone moiety of compactin and mevinolin.

The high-pressure [4+2]cycloaddition of 1-methoxybuta-1,3-diene to the glycolaldehyde-derived heterodienophiles, catalyzed by chiral metallosalen complexes

A high-pressure (ca. 10 kbar) reaction of 1-methoxybuta-1,3-diene 1 with variously O-protected glycolaldehydes 2, catalyzed by the chiral (salen)Cr(III)Cl 4a-d and 5 or (salen)Co(II) 6a-f and 7 complexes, has been studied. The best results were obtained for tert- butyldimethylsilyloxyacetaldehyde 2a. The reaction afforded, in good yield (up to 90%) and with very good diastereoselectivity (up to 92%) and enantioselectivity (up to 93% ee), the [4+2]cycloadducts 3a, which are compounds of significant synthetic interest. The stereochemical model of the cycloaddition reaction is discussed.

Synthesis of 4-deoxy-L-(and D-)hexoses from chiral noncarbohydrate building blocks

4-Deoxy-L-hexoses were synthesized starting from our previously reported reagent 1 and (R)-benzyl glycidyl ether, which led in few steps to a substituted dihydropyran 6. The stereocontrolled hydroxylation of the latter afforded the corresponding 4-deoxy-L

Stereochemical course of the [4+2] cycloaddition of 1-methoxybuta-1,3-diene to N-glyoxyloyl-(2R)-bornane-10,2-sultam. The formal synthesis of compactin and mevinolin

The chiral heterodienophile N-glyoxyloyl-(2R)-bornane-10,2-sultam 2, readily prepared from (2R)-bornane-10,2-sultam 1, was used in noncatalyzed atmospheric and high-pressure as well as in [Eu(fod)3]-catalyzed [4+2] cycloadditions with 1-methoxybuta-1,3-diene 3. All the [4+2] cycloadditions studied led to diastereoisomeric mixtures of 6-substituted derivatives of 2-methoxy-5,6-dihydro-2H-pyran 4-7. The extent of asymmetric induction in these reactions was established by 1H NMR analysis and the absolute configuration of the thermodynamically stable products 5 and 7 by X-ray analysis, and independently by chemical correlation. Stereochemical models for both noncatalyzed and [Eu(fod3]-promoted reactions are proposed. The [4+2] cycloadduct 5 was then effectively transformed into (4R)-hydroxy-(6S)-hydroxymethyltetrahydropyrone-2 12, a key synthon for the lactone moiety of compactin 10 and mevinolin 11.

Asymmetric catalysis of Diels-Alder cycloadditions by an MS-free binaphthol-titanium complex: Dramatic effect of MS, linear vs positive nonlinear relationship, and synthetic applications

Asymmetric Diets-Aider (D.-A.) reaction of 5-hydroxynaphthoquinone (juglone) with butadienyl acetate catalyzed by the binaphthol-derived chiral titanium (BINOL-Ti) complex 1 proceeds in only 9% ee in the presence of molecular sieves (MS). Remarkably, however, this reaction proceeds in 76-96% ee with BINOL-Ti complex 1 freed from MS to provide the endo-adducts useful for the synthesis of anthracyclines and tetracyclines. The solid MS-free BINOL-Ti complex 1 is stable for months at -20°C. Enhancements in endo selectivity and asymmetric induction are observed with the MS-free BINOL-Ti 1 also in the catalyzed D.-A. cycloaddition of methacrolein and glyoxylate with 1,3-dienol ethers and esters. The glyoxylate adducts can be converted to the mevinolin (compactin) intermediates. Surprisingly, the MS-free complex 1 exhibits not only a linear relationship between the ee's of BINOL-Ti 1 and the D.-A. products but also a positive nonlinear effect (asymmetric amplification), depending simply on the mixing manner of (R)-1 with (S)-1 or (±)-1.