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Literature DB >> 17295500

Beta-silylated homopropargylic amines via the asymmetric allenylboration of aldimines.

Abstract

The asymmetric synthesis of alpha-trimethylsilylpropargylic carbamines (7) through the addition of allenylboranes 4 to N-H aldimines is reported. The insertion of TMSCHN2 into enantiomerically pure B-alkynyl-10-TMS-9-borabicyclo[3.3.2]decanes 3 followed by a sterically driven 1,3-suprafacial borotropic shift proceeds with complete stereospecificity to produce 4 in diastereomerically and enantiomerically pure form. These reagents give 7 (51-85%, syn/anti >99%, 92-9% ee) permitting the recovery of 8 (53-63%). Allenylboranes 4 also provide a convenient route to optically pure allenylsilanes 13 (55-94%) through their protonolysis. [reaction: see text]

Entities: Chemical Gene

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Year: 2007 PMID： 17295500 DOI： 10.1021/ol070074g

Source DB: PubMed Journal: Org Lett ISSN： 1523-7052 Impact factor: 6.005

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Cited

8 in total

1. Lewis Acid Catalyzed Borotropic Shifts in the Design of Diastereo- and Enantioselective γ-Additions of Allylboron Moieties to Aldimines.

Authors: Farid W van der Mei; Hiroshi Miyamoto; Daniel L Silverio; Amir H Hoveyda
Journal: Angew Chem Int Ed Engl Date: 2016-03-09 Impact factor: 15.336

2. Thermodynamic control of 1,3-boratropic shifts of α- and γ-stannyl-substituted allylboranes: hyperconjugation outweighs steric effects.

Authors: Preston S Stewart; Ming Chen; William R Roush; Daniel H Ess
Journal: Org Lett Date: 2011-02-16 Impact factor: 6.005

3. Enantioselective synthesis of (E)-delta-stannyl homoallylic alcohols via aldehyde allylboration using alpha-stannylallylboranes generated by allene hydroboration followed by a highly diastereoselective 1,3-boratropic shift.

Authors: Ming Chen; Daniel H Ess; William R Roush
Journal: J Am Chem Soc Date: 2010-06-16 Impact factor: 15.419

4. Asymmetric synthesis of 2 degrees- and 3 degrees-Carbinols via B-methallyl-10-(TMS and Ph)-9-borabicyclo[3.3.2]decanes.

Authors: José G Roman; John A Soderquist
Journal: J Org Chem Date: 2007-11-14 Impact factor: 4.354

5. Synthesis of enantioenriched homopropargylic sulfonamides by a three component reaction of aldehydes, sulfonamides, and chiral allenylsilanes.

Authors: Ryan A Brawn; James S Panek
Journal: Org Lett Date: 2009-10-01 Impact factor: 6.005

Beta-silylated homopropargylic amines via the asymmetric allenylboration of aldimines.

1. Lewis Acid Catalyzed Borotropic Shifts in the Design of Diastereo- and Enantioselective γ-Additions of Allylboron Moieties to Aldimines.

2. Thermodynamic control of 1,3-boratropic shifts of α- and γ-stannyl-substituted allylboranes: hyperconjugation outweighs steric effects.

3. Enantioselective synthesis of (E)-delta-stannyl homoallylic alcohols via aldehyde allylboration using alpha-stannylallylboranes generated by allene hydroboration followed by a highly diastereoselective 1,3-boratropic shift.

4. Asymmetric synthesis of 2 degrees- and 3 degrees-Carbinols via B-methallyl-10-(TMS and Ph)-9-borabicyclo[3.3.2]decanes.

5. Synthesis of enantioenriched homopropargylic sulfonamides by a three component reaction of aldehydes, sulfonamides, and chiral allenylsilanes.

6. Quantum-mechanical study of 10-R-9-borabicyclo[3.3.2]decane alkene hydroboration.

7. A Simple Procedure for the Synthesis of β-Hydroxyallenamides via Homoallenylation of Aldehydes.

8. Silver-Catalyzed Enantioselective Propargylation Reactions of N-Sulfonylketimines.