Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2022 Aug 19;87(16):11237-11252.
doi: 10.1021/acs.joc.2c01170. Epub 2022 Jul 28.

Highly Stereospecific Cyclizations of Homoallylic Silanols

Anand H Shinde  1 , Ranjeet A Dhokale  1 , Joel T Mague  2 , Shyam Sathyamoorthi  1
Affiliations

Highly Stereospecific Cyclizations of Homoallylic Silanols

Anand H Shinde et al. J Org Chem. .

Abstract

We demonstrate that di-tert-butylsilanols are competent nucleophiles for the intramolecular interception of palladium π-allyl species. In these reactions, allyl ethyl carbonates are the best precursors for the formation of palladium π-allyl intermediates, and [(Cinnamyl)PdCl]2/BINAP is superior to other Pd salt/ligand framework combinations. Our optimized protocol is compatible with a variety of silanol substrates. Importantly, the cyclization is perfectly stereospecific, proceeding via an anti-syn mechanism, which stands in contrast to reported analogous reactions of alcohols and phenols, known to proceed via an anti-anti mechanism. The alkenes in the product dioxasilinanes serve as blank slates for further functionalization.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1.
Scheme 1.
(A) Polyhydroxylated and Stereochemically Complex Biologically Active Molecules and (B) Potentially Mild and Highly Selective Method for Protected 1,3-Diol Formation
Scheme 2.
Scheme 2.
Typical Sequence for Starting Material Preparation
Scheme 3.
Scheme 3.
Examination of Leaving Group Effects
Scheme 4.
Scheme 4.
Substrate Scope with Primary Silanols
Scheme 5.
Scheme 5.
Substrate Scope with Secondary Silanols
Scheme 6.
Scheme 6.
(A) Determination of the Stereochemistry of Linear Starting Materials and (B) Mechanistic Hypothesis
Scheme 7.
Scheme 7.
Product Alkenyl Dioxasilinanes Being Convenient Synthons for Many Transformations Including (A) Cross-Metathesis and (B) Dihydroxylation
See this image and copyright information in PMC

References

    1. Correa A; García Mancheño O; Bolm C Iron-catalysed carbon–heteroatom and heteroatom–heteroatom bond forming processes. Chem. Soc. Rev 2008, 37, 1108–1117. - PubMed
    1. Hartwig JF Carbon–heteroatom bond formation catalysed by organometallic complexes. Nature 2008, 455, 314–322. - PMC - PubMed
    1. Hosoya K; Odagi M; Nagasawa K Guanidine organocatalysis for enantioselective carbon-heteroatom bond-forming reactions. Tetrahedron Lett. 2018, 59, 687–696.
    1. Puleo TR; Sujansky SJ; Wright SE; Bandar JS Organic Superbases in Recent Synthetic Methodology Research. Chem. - Eur. J 2021, 27, 4216–4229. - PubMed
    1. Hong AY; Stoltz BM The Construction of All-Carbon Quaternary Stereocenters by Use of Pd-Catalyzed Asymmetric Allylic Alkylation Reactions in Total Synthesis. Eur. J. Org. Chem 2013, 2013, 2745–2759. - PMC - PubMed

Publication types