The total synthesis of (-)-aplysin via a lithiation-borylation-propenylation sequence

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

doi:10.1016/j.tet.2012.05.095

The total synthesis of (-)-aplysin via a lithiation-borylation-propenylation sequence

Catherine J. Fletcher, Daniel J. Blair, 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

30 Citations (Scopus)

Abstract

A concise, highly enantioselective synthesis of sesquiterpene natural products (-)-debromoaplysin and (-)-aplysin has been completed. The key steps included lithiation-borylation of a secondary benzylic carbamate to give a tertiary boronic ester followed by propenylation which installed the quaternary stereocenter with complete enantioselectivity. Subsequent RCM followed by deprotection and in situ cyclization led to debromoaplysin with good diastereoselectivity from which the target compound was prepared in just eight overall steps. (C) 2012 Elsevier Ltd. All rights reserved.

Original language	English
Pages (from-to)	7598-7604
Number of pages	7
Journal	Tetrahedron
Volume	68
Issue number	37
DOIs	https://doi.org/10.1016/j.tet.2012.05.095
Publication status	Published - 16 Sept 2012

Keywords

Lithiation-borylation
Quaternary stereocenter
Aplysin
Total synthesis
Sesquiterpene
ASYMMETRIC TRANSFER HYDROGENATION
RING-CLOSING METATHESIS
FORMAL TOTAL-SYNTHESIS
LAURENCIA-FILIFORMIS
OLEFIN METATHESIS
(-)-DEBROMOAPLYSIN
ENANTIOSELECTIVITY
SESQUITERPENES
ALCOHOLS
APLYSIN

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GENERAL AND CONVERGENT STRATEGY FOR ASYMMETRIC SYNTHESIS
Aggarwal, V. K. (Principal Investigator)
1/10/07 → 1/04/13
Project: Research
NEW ASSYMETRIC REACTIONS AND THEIR APPLICATION IN TOTAL SYNTHESIS
Aggarwal, V. K. (Principal Investigator)
1/10/05 → 1/10/10
Project: Research

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@article{8c0f7b842e744b659cdbea72514cd40d,

title = "The total synthesis of (-)-aplysin via a lithiation-borylation-propenylation sequence",

abstract = "A concise, highly enantioselective synthesis of sesquiterpene natural products (-)-debromoaplysin and (-)-aplysin has been completed. The key steps included lithiation-borylation of a secondary benzylic carbamate to give a tertiary boronic ester followed by propenylation which installed the quaternary stereocenter with complete enantioselectivity. Subsequent RCM followed by deprotection and in situ cyclization led to debromoaplysin with good diastereoselectivity from which the target compound was prepared in just eight overall steps. (C) 2012 Elsevier Ltd. All rights reserved.",

keywords = "Lithiation-borylation, Quaternary stereocenter, Aplysin, Total synthesis, Sesquiterpene, ASYMMETRIC TRANSFER HYDROGENATION, RING-CLOSING METATHESIS, FORMAL TOTAL-SYNTHESIS, LAURENCIA-FILIFORMIS, OLEFIN METATHESIS, (-)-DEBROMOAPLYSIN, ENANTIOSELECTIVITY, SESQUITERPENES, ALCOHOLS, APLYSIN",

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

year = "2012",

month = sep,

day = "16",

doi = "10.1016/j.tet.2012.05.095",

language = "English",

volume = "68",

pages = "7598--7604",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier",

number = "37",

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TY - JOUR

T1 - The total synthesis of (-)-aplysin via a lithiation-borylation-propenylation sequence

AU - Fletcher, Catherine J.

AU - Blair, Daniel J.

AU - Wheelhouse, Katherine M. P.

AU - Aggarwal, Varinder K.

PY - 2012/9/16

Y1 - 2012/9/16

N2 - A concise, highly enantioselective synthesis of sesquiterpene natural products (-)-debromoaplysin and (-)-aplysin has been completed. The key steps included lithiation-borylation of a secondary benzylic carbamate to give a tertiary boronic ester followed by propenylation which installed the quaternary stereocenter with complete enantioselectivity. Subsequent RCM followed by deprotection and in situ cyclization led to debromoaplysin with good diastereoselectivity from which the target compound was prepared in just eight overall steps. (C) 2012 Elsevier Ltd. All rights reserved.

AB - A concise, highly enantioselective synthesis of sesquiterpene natural products (-)-debromoaplysin and (-)-aplysin has been completed. The key steps included lithiation-borylation of a secondary benzylic carbamate to give a tertiary boronic ester followed by propenylation which installed the quaternary stereocenter with complete enantioselectivity. Subsequent RCM followed by deprotection and in situ cyclization led to debromoaplysin with good diastereoselectivity from which the target compound was prepared in just eight overall steps. (C) 2012 Elsevier Ltd. All rights reserved.

KW - Lithiation-borylation

KW - Quaternary stereocenter

KW - Aplysin

KW - Total synthesis

KW - Sesquiterpene

KW - ASYMMETRIC TRANSFER HYDROGENATION

KW - RING-CLOSING METATHESIS

KW - FORMAL TOTAL-SYNTHESIS

KW - LAURENCIA-FILIFORMIS

KW - OLEFIN METATHESIS

KW - (-)-DEBROMOAPLYSIN

KW - ENANTIOSELECTIVITY

KW - SESQUITERPENES

KW - ALCOHOLS

KW - APLYSIN

U2 - 10.1016/j.tet.2012.05.095

DO - 10.1016/j.tet.2012.05.095

M3 - Article (Academic Journal)

SN - 0040-4020

VL - 68

SP - 7598

EP - 7604

JO - Tetrahedron

JF - Tetrahedron

IS - 37

ER -

The total synthesis of (-)-aplysin via a lithiation-borylation-propenylation sequence

Abstract

Keywords

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Projects

GENERAL AND CONVERGENT STRATEGY FOR ASYMMETRIC SYNTHESIS

NEW ASSYMETRIC REACTIONS AND THEIR APPLICATION IN TOTAL SYNTHESIS

Cite this