Journal ArticleDOI
Tandem Zn-Brook Rearrangement/Ene-Allene Carbocyclization†
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TLDR
The addition of metalated alkynes to acylsilanes leads to the corresponding α-propargyl-silanol derivatives, which undergo cyclization to give functionalized carbocycles as single diastereoisomers as discussed by the authors.About:
This article is published in European Journal of Organic Chemistry.The article was published on 2009-04-01. It has received 14 citations till now. The article focuses on the topics: Brook rearrangement & Ene reaction.read more
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Acylsilanes: valuable organosilicon reagents in organic synthesis
TL;DR: This review provides an overview of the recent advances in the synthesis and application of acylsilanes in organic chemistry, with a particular focus on the progress made in the last two decades.
Journal ArticleDOI
One‐Pot Zinc‐Promoted Asymmetric Alkynylation/Brook‐Type Rearrangement/Ene–Allene Cyclization: Highly Selective Formation of Three New Bonds and Two Stereocenters in Acyclic Systems
Polina Smirnov,Jomon Mathew,Anne Nijs,Einat Katan,Miriam Karni,Carsten Bolm,Yitzhak Apeloig,Ilan Marek +7 more
TL;DR: It's as easy as 1, 2, 3: In a one-pot sequence, two stereocenters and three new bonds were created with high selectivity through an asymmetric alkynylation of acyl silanes, a tandem Brook-type rearrangement and Zn-ene-allene cyclization, the addition of an electrophile, and finally oxidation.
Journal ArticleDOI
Enantioselective synthesis of siloxyallenes from alkynoylsilanes by reduction and a Brook rearrangement and their subsequent trapping in a [4+2] cycloaddition.
TL;DR: In this article, a consecutive process is developed for the enantioselective formation of siloxyallenes such as (II) from alkynoylsilanes (I), taking advantage of reduction by a chiral lithium amide followed by a SE′-type process through the Brook rearrangement of an alkynyl silicate intermediate.
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Iterative Dianion Relay Along the Ring: Formation of gem‐Bis(trimethylsilyl) Cyclopentenones from 2,5‐Bis(trimethylsilyl) Oxy‐cyclopentadienyl Dianions and Acid Chlorides
TL;DR: In this paper, anion relay chemistry (ARC) has been demonstrated to be useful for high-efficient and facile synthesis of structurally complex scaffolds, which can be used for the design and development of new linchpins.
Journal ArticleDOI
Formation of three new bonds and two stereocenters in acyclic systems by zinc-mediated enantioselective alkynylation of acylsilanes, Brook rearrangement, and ene-allene carbocyclization reactions.
Polina Smirnov,Einat Katan,Jomon Mathew,Arseni Kostenko,Miriam Karni,Anne Nijs,Carsten Bolm,Yitzhak Apeloig,Ilan Marek +8 more
TL;DR: Diastereoisomerically pure and enantiomerically enriched substituted propargyl diols possessing a tertiary hydroxyl group were synthesized in a single-pot operation through a combined catalytic enantioselective alkynylation of acylsilanes, followed by an allenyl-Zn-Brook rearrangement and Zn-ene-allene cyclization reaction.
References
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[2,3]-Wittig sigmatropic rearrangements in organic synthesis
Takeshi Nakai,Koichi Mikami +1 more
Journal ArticleDOI
Creation of quaternary stereocenters in carbonyl allylation reactions
Ilan Marek,Genia Sklute +1 more
TL;DR: The most powerful approaches to the creation of quaternary stereocenters in the addition of 3,3'-disubstituted allylmetals to aldehydes are described.