Stereocontrolled Synthesis of Adjacent Acyclic Quaternary-Tertiary Motifs: Application to a Concise Total Synthesis of (-)-Filiformin

Daniel J. Blair; Catherine J. Fletcher; Katherine M. P. Wheelhouse; Varinder K. Aggarwal

doi:10.1002/anie.201400944

Stereocontrolled Synthesis of Adjacent Acyclic Quaternary-Tertiary Motifs: Application to a Concise Total Synthesis of (-)-Filiformin

Daniel J. Blair, Catherine J. Fletcher, Katherine M. P. Wheelhouse, Varinder K. Aggarwal^*

^*Corresponding author for this work

School of Chemistry

Research output: Contribution to journal › Article (Academic Journal) › peer-review

44 Citations (Scopus)

533 Downloads (Pure)

Abstract

Lithiation/borylation methodology has been developed for the synthesis of acyclic quaternary-tertiary motifs with full control of relative and absolute stereochemistry, thus leading to all four possible isomers of a stereodiad. A novel intramolecular Zweifel-type olefination enabled acyclic stereocontrol to be transformed into cyclic stereocontrol. These key steps have been applied to the shortest enantioselective synthesis of (-)-filiformin to date (9 steps) with full stereocontrol.

Original language	English
Pages (from-to)	5552-5555
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	53
Issue number	22
Early online date	22 Apr 2014
DOIs	https://doi.org/10.1002/anie.201400944
Publication status	Published - May 2014

Research Groups and Themes

Organic & Biological

Keywords

boron
enantioselectivity
lithium
natural products
total synthesis
REAGENT-CONTROLLED HOMOLOGATION
BORONIC ESTERS
SECONDARY ALCOHOLS
ENANTIOSELECTIVE CONSTRUCTION
STEREOSELECTIVE CONSTRUCTION
ELECTROPHILIC SUBSTITUTION
(+)-SPARTEINE SURROGATE
ASYMMETRIC-SYNTHESIS
STEREOCENTERS
BORYLATION

Access to Document

10.1002/anie.201400944

DBlair_ACIE_2014
This is the accepted version of the following article:Blair, D. J., Fletcher, C. J., Wheelhouse, K. M. P. and Aggarwal, V. K. (2014), Stereocontrolled Synthesis of Adjacent Acyclic Quaternary-Tertiary Motifs: Application to a Concise Total Synthesis of (−)-Filiformin. Angew. Chem. Int. Ed., 53: 5552–5555. doi: 10.1002/anie.201400944, which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/anie.201400944/abstract
Accepted author manuscript, 801 KB

http://onlinelibrary.wiley.com/doi/10.1002/anie.201400944/abstract

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Changing the Synthesis Landscape with Boron at the Helm: from Chiral Organometallics to Assembly Line Synthesis
Aggarwal, V. K. (Principal Investigator)
14/05/12 → 13/01/18
Project: Research

Cite this

@article{6866a18867f941f499402749bb788b48,

title = "Stereocontrolled Synthesis of Adjacent Acyclic Quaternary-Tertiary Motifs: Application to a Concise Total Synthesis of (-)-Filiformin",

abstract = "Lithiation/borylation methodology has been developed for the synthesis of acyclic quaternary-tertiary motifs with full control of relative and absolute stereochemistry, thus leading to all four possible isomers of a stereodiad. A novel intramolecular Zweifel-type olefination enabled acyclic stereocontrol to be transformed into cyclic stereocontrol. These key steps have been applied to the shortest enantioselective synthesis of (-)-filiformin to date (9 steps) with full stereocontrol.",

keywords = "boron, enantioselectivity, lithium, natural products, total synthesis, REAGENT-CONTROLLED HOMOLOGATION, BORONIC ESTERS, SECONDARY ALCOHOLS, ENANTIOSELECTIVE CONSTRUCTION, STEREOSELECTIVE CONSTRUCTION, ELECTROPHILIC SUBSTITUTION, (+)-SPARTEINE SURROGATE, ASYMMETRIC-SYNTHESIS, STEREOCENTERS, BORYLATION",

author = "Blair, \{Daniel J.\} and Fletcher, \{Catherine J.\} and Wheelhouse, \{Katherine M. P.\} and Aggarwal, \{Varinder K.\}",

year = "2014",

month = may,

doi = "10.1002/anie.201400944",

language = "English",

volume = "53",

pages = "5552--5555",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley \& Sons, Ltd.",

number = "22",

}

Stereocontrolled Synthesis of Adjacent Acyclic Quaternary-Tertiary Motifs: Application to a Concise Total Synthesis of (-)-Filiformin. / Blair, Daniel J.; Fletcher, Catherine J.; Wheelhouse, Katherine M. P. et al.
In: Angewandte Chemie - International Edition, Vol. 53, No. 22, 05.2014, p. 5552-5555.

Research output: Contribution to journal › Article (Academic Journal) › peer-review

TY - JOUR

T1 - Stereocontrolled Synthesis of Adjacent Acyclic Quaternary-Tertiary Motifs

T2 - Application to a Concise Total Synthesis of (-)-Filiformin

AU - Blair, Daniel J.

AU - Fletcher, Catherine J.

AU - Wheelhouse, Katherine M. P.

AU - Aggarwal, Varinder K.

PY - 2014/5

Y1 - 2014/5

N2 - Lithiation/borylation methodology has been developed for the synthesis of acyclic quaternary-tertiary motifs with full control of relative and absolute stereochemistry, thus leading to all four possible isomers of a stereodiad. A novel intramolecular Zweifel-type olefination enabled acyclic stereocontrol to be transformed into cyclic stereocontrol. These key steps have been applied to the shortest enantioselective synthesis of (-)-filiformin to date (9 steps) with full stereocontrol.

AB - Lithiation/borylation methodology has been developed for the synthesis of acyclic quaternary-tertiary motifs with full control of relative and absolute stereochemistry, thus leading to all four possible isomers of a stereodiad. A novel intramolecular Zweifel-type olefination enabled acyclic stereocontrol to be transformed into cyclic stereocontrol. These key steps have been applied to the shortest enantioselective synthesis of (-)-filiformin to date (9 steps) with full stereocontrol.

KW - boron

KW - enantioselectivity

KW - lithium

KW - natural products

KW - total synthesis

KW - REAGENT-CONTROLLED HOMOLOGATION

KW - BORONIC ESTERS

KW - SECONDARY ALCOHOLS

KW - ENANTIOSELECTIVE CONSTRUCTION

KW - STEREOSELECTIVE CONSTRUCTION

KW - ELECTROPHILIC SUBSTITUTION

KW - (+)-SPARTEINE SURROGATE

KW - ASYMMETRIC-SYNTHESIS

KW - STEREOCENTERS

KW - BORYLATION

U2 - 10.1002/anie.201400944

DO - 10.1002/anie.201400944

M3 - Article (Academic Journal)

C2 - 24757079

SN - 1433-7851

VL - 53

SP - 5552

EP - 5555

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 22

ER -

Stereocontrolled Synthesis of Adjacent Acyclic Quaternary-Tertiary Motifs: Application to a Concise Total Synthesis of (-)-Filiformin

Abstract

Research Groups and Themes

Keywords

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Projects

Changing the Synthesis Landscape with Boron at the Helm: from Chiral Organometallics to Assembly Line Synthesis

Cite this