62296-04-2

Upstream product

• 873-49-4 cyclopropylbenzene 
• 563-68-8 thallium(I) acetate 
• 132836-85-2 (1R,5S,3Z)-1-acetoxy-5-benzyloxy-1-phenyl-3-hexene 
• 119204-58-9 (4S,2E)-4-Phenylmethoxypent-2-enyl(tributyl)stannane 
• 132836-59-0 (1R,5S,3Z)-5-benzyloxy-1-phenylhex-3-en-1-ol 
• 100-52-7 benzaldehyde 
• 1384833-85-5 (1R,5S,3Z)-1-acetoxy-5-(N,N-dibenzylamino)-1-phenylhex-3-ene 
• 155626-76-9 (1R,5S,3Z)-5-(N,N-dibenzylamino)-1-phenylhex-3-en-1-ol 

Downstream Products

• 103574-68-1 (R)-1-phenylpropane-1,3-diol mono-t-butyldimethylsilyl ether 
• 156327-45-6 (1R)-1-acetoxy-3-tert-butyldimethylsilyloxypropane 

Relevant academic research and scientific papers

1,5-Stereocontrol in tin(IV) halide mediated reactions between N- and S-substituted pent-2-enylstannanes and aldehydes or imines

Following transmetalation of (4S)-4-(dibenzylamino)pent-2-enyl(tributyl) stannane with tin(IV) bromide, reactions of the resulting allyltin tribromide with aldehydes gave (3Z)-1,5-syn-5-(dibenzylamino)hex-3-en-1-ols with excellent, ca. 98:2, stereocontrol. (4R)-5-Benzylthio-4-methylpent-2-enyl(tributyl) stannane similarly reacted with aldehydes to give (3Z)-1,5-anti-6-benzylthio-5- methylhex-3-en-1-ols with 87:13 stereocontrol. Although the analogous reaction of (4R)-4-benzylthiopent-2-enyl(tributyl)stannane with benzaldehyde proceeded with some stereoselectivity, 80-90:20-10, in favour of the (3Z)-1,5-syn- diastereoisomer, the yield was low due to a competing Lewis acid catalysed 1,4-elimination. N-Acylamino- and S-acylthio-pent-2-enylstannanes reacted with aldehydes with variable syn/anti-stereoselectivities. Tin(IV) chloride promoted reactions of the 4-(dibenzylamino)pent-2-enylstannane with 1- alkoxycarbonylimines gave (E)-alk-4-enoates with a modest preference for the 2,6-anti-products, 2,6-anti/2,6-syn=75:25.

Effective 1,5-, 1,6- and 1,7-remote stereocontrol in reactions of alkoxy- and hydroxy-substituted allylstannanes with aldehydes

Alk-2-enylstannanes with 4-, 5- and 6-alkoxy- or -hydroxy-substituents are transmetallated stereoselectively with tin(iv) halides to generate allyltin trihalides which react with aldehydes to give (Z)-alk-3-enols with useful levels of 1,5-, 1,6- and 1,7-stereocontrol. Alk-2-enylstannanes with a stereogenic centre bearing a hydroxy or alkoxy group at the 4-, 5- or 6-position, react with overall (Z)-1,5-, 1,6- and 1,7-syn-stereoselectivity with respect to the hydroxy and alkoxy substituents. The analogous reactions of alkoxy- and -hydroxyalk-2-enylstannanes with a methyl bearing stereogenic centre at the 4- or 5-position react with overall (Z)-1,5- and 1,6-anti-stereoselectivity with respect to the hydroxy and methyl substituents.

1,9-Stereocontrol from 1,7-induction using an allylstannane followed by an Ireland-Claisen rearrangement

The 6-hydroxynona-2,7-dienylstananne 10 reacts with aldehydes after transmetallation with tin(IV) bromide with syn-selective 1,7-induction (1,7- syn : 1,7-anti = ca. 90 : 10). Ireland-Claisen rearrangements of the acetates 28a,b prepared from the syn-benz

Stereoselective synthesis of 2-(1-alkoxyalkyl)-3-hydroxy-5-substituted- tetrahydrofurans

Oxidation of toluene-p-sulfonates derived from 1-substituted-1,5-syn-5- benzyloxyhex-3-enols using osmium tetraoxide gives stereoselective access to 2-(1-alkoxyalkyl)-3-hydroxy-5-substituted-tetrahydrofurans. This procedure has been applied to synthesize bistetrahydrofurans.

1,6-Asymmetric induction in reactions between 6-hydroxy-6-methylhex-2-enyl(tributyl)stannane and aldehydes promoted by tin(IV) bromide

(R)-6-Hydroxy-5-methylhex-2-enyl(tributyl)stannane 4 transmetallates on treatment with tin(IV) bromide to give an intermediate allyltin tribromide which reacts with aldehydes to give 1-substituted (Z)-6-methylhept-2-ene-1,7-diols 7 with excellent anti-1,6

Effective 1,5-asymmetric induction in tin(IV) chloride promoted reactions between aldehydes and (4-alkoxy-2-alkenyl)tributylstannanes

Transmetallation of (S)-4-benzyloxy-2-pentenyl(tributyl)stannane (1) using tin(IV) chloride generates an allyltin trichloride which reacts in situ with aldehydes to give 1-substituted syn-(3Z)-5-benzyloxyhexenols with excellent stereoselectivity. With chiral aldehydes, the stereoselectivity of the reaction is dominated by the reagent, except for 2-alkoxyaldehydes which show matching and mismatching consistent with preferred Felkin-Anh diastereofacial selectivity.

1,6-asymmetric induction in Lewis acid promoted reactions of ε - methoxy- and ε -hydroxy-allylstannanes and aldehydes

Allylstannanes with an ε -methoxy or ε -hydroxy substituent undergo reactions with aldehydes promoted by tin(IV)bromide to give syn-1,6-diol derivatives with useful regio- and stereoselectivity.

1,5-Asymmetric induction in reactions between δ-alkoxyallylstannanes and aldehydes induced by tin (IV) chloride

Treatment of (S)-4-benzyloxypent-(2E)-2-enyl(tributyl)stannane (3) with tin (IV) chloride at -78°C, followed by the addition of an aldehyde, gives 1,5-diol derivatives (6) with excellent 1,5-diastereoselectivity.