Rh-catalyzed desymmetrization of α-quaternary centers by isomerization-hydroacylation

Jung Woo Park; Kevin G.M. Kou; Daniel K. Kim; Vy M. Dong

doi:10.1039/c5sc01553g

Rh-catalyzed desymmetrization of α-quaternary centers by isomerization-hydroacylation

Jung Woo Park, Kevin G.M. Kou, Daniel K. Kim, Vy M. Dong

Dept. of Fine Chemistry

University of California at Irvine

Research output: Contribution to journal › Article › peer-review

49 Scopus citations

Abstract

We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C-H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopentanones. Mechanistic studies support irreversible and enantioselective olefin-isomerization followed by olefin-hydroacylation.

Original language	English
Pages (from-to)	4479-4483
Number of pages	5
Journal	Chemical Science
Volume	6
Issue number	8
DOIs	https://doi.org/10.1039/c5sc01553g
State	Published - 1 Aug 2015

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title = "Rh-catalyzed desymmetrization of α-quaternary centers by isomerization-hydroacylation",

abstract = "We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C-H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopentanones. Mechanistic studies support irreversible and enantioselective olefin-isomerization followed by olefin-hydroacylation.",

author = "Park, \{Jung Woo\} and Kou, \{Kevin G.M.\} and Kim, \{Daniel K.\} and Dong, \{Vy M.\}",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

year = "2015",

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doi = "10.1039/c5sc01553g",

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volume = "6",

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journal = "Chemical Science",

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T1 - Rh-catalyzed desymmetrization of α-quaternary centers by isomerization-hydroacylation

AU - Park, Jung Woo

AU - Kou, Kevin G.M.

AU - Kim, Daniel K.

AU - Dong, Vy M.

PY - 2015/8/1

Y1 - 2015/8/1

N2 - We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C-H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopentanones. Mechanistic studies support irreversible and enantioselective olefin-isomerization followed by olefin-hydroacylation.

AB - We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C-H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopentanones. Mechanistic studies support irreversible and enantioselective olefin-isomerization followed by olefin-hydroacylation.

UR - https://www.scopus.com/pages/publications/84937131564

U2 - 10.1039/c5sc01553g

DO - 10.1039/c5sc01553g

M3 - Article

AN - SCOPUS:84937131564

SN - 2041-6520

VL - 6

SP - 4479

EP - 4483

JO - Chemical Science

JF - Chemical Science

IS - 8

ER -

Rh-catalyzed desymmetrization of α-quaternary centers by isomerization-hydroacylation

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