Synfacts 2014; 10(1): 0079
DOI: 10.1055/s-0033-1340369
Metal-Mediated Synthesis
© Georg Thieme Verlag Stuttgart · New York

Stereoselective Synthesis of syn-β-Hydroxy-α-vinyl Carboxylate Esters

Contributor(s):
Paul Knochel
,
Andreas K. Steib
Kister J, Ess DH, Roush WR * Scripps Florida, Jupiter and Brigham Young University, Provo, USA
Enantio- and Diastereoselective Synthesis of syn-β-Hydroxy-α-vinyl Carboxylic Esters via Reductive Aldol Reactions of Ethyl Allenecarboxylate with 10-TMS-9-Borabicyclo[3.3.2]decane and DFT Analysis of the Hydroboration Pathway.

Org. Lett. 2013;
15: 5436-5439
Further Information

Publication History

Publication Date:
13 December 2013 (online)

 

Significance

The authors report a novel enantio- and diastereoselective synthesis of syn-β-hydroxy-α-vinyl carboxylate esters. The reaction proceeds via a reductive aldol reaction of an ethyl ­allene ­carboxylate with 10-TMS-9-borabicyclo[3.3.2]-decane.


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Comment

The exclusive formation of syn-β-hydroxy-α-vinyl carboxylate esters can be explained by an aldol reaction via a chair-like transition state. DFT calculations suggest that the allene hydroboration involves a 1,4-reduction of the ethyl allene carboxylate with 10-TMS-9-borabicyclo-[3.3.2]decane.


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