Synthesis of spirocyclic orthoesters by 'anomalous' rhodium(II)-catalysed intramolecular C-H insertions

Fanny J. Lombard; Romain J. Lepage; Brett D. Schwartz; Ryne C. Johnston; Peter C. Healy; Elizabeth H. Krenske; Mark J. Coster

doi:10.1039/c7ob02123b

Synthesis of spirocyclic orthoesters by 'anomalous' rhodium(II)-catalysed intramolecular C-H insertions

Fanny J. Lombard, Romain J. Lepage, Brett D. Schwartz, Ryne C. Johnston, Peter C. Healy, Elizabeth H. Krenske, Mark J. Coster^*

^*Corresponding author for this work

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

8 Citations (Scopus)

Abstract

A tetrahydropyranyl acetal bearing a proximal phenyl diazoketone substituent underwent Rh(ii)-catalysed C-H insertion via an 'anomalous' C-O bond-forming, rather than C-C bond-forming, transformation, giving spirocyclic orthoesters. Density functional theory calculations with M06 show that the formation of these anomalous products involves hydride transfer to the rhodium carbene, giving an intermediate zwitterion which undergoes C-O bond formation in preference to C-C bond formation.

Original language	English
Pages (from-to)	256-261
Number of pages	6
Journal	Organic and Biomolecular Chemistry
Volume	16
Issue number	2
DOIs	https://doi.org/10.1039/c7ob02123b
Publication status	Published - 2018
Externally published	Yes

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title = "Synthesis of spirocyclic orthoesters by 'anomalous' rhodium(II)-catalysed intramolecular C-H insertions",

abstract = "A tetrahydropyranyl acetal bearing a proximal phenyl diazoketone substituent underwent Rh(ii)-catalysed C-H insertion via an 'anomalous' C-O bond-forming, rather than C-C bond-forming, transformation, giving spirocyclic orthoesters. Density functional theory calculations with M06 show that the formation of these anomalous products involves hydride transfer to the rhodium carbene, giving an intermediate zwitterion which undergoes C-O bond formation in preference to C-C bond formation.",

author = "Lombard, \{Fanny J.\} and Lepage, \{Romain J.\} and Schwartz, \{Brett D.\} and Johnston, \{Ryne C.\} and Healy, \{Peter C.\} and Krenske, \{Elizabeth H.\} and Coster, \{Mark J.\}",

note = "Publisher Copyright: {\textcopyright} 2017 The Royal Society of Chemistry.",

year = "2018",

doi = "10.1039/c7ob02123b",

language = "English",

volume = "16",

pages = "256--261",

journal = "Organic and Biomolecular Chemistry",

issn = "1477-0520",

publisher = "Royal Society of Chemistry",

number = "2",

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TY - JOUR

T1 - Synthesis of spirocyclic orthoesters by 'anomalous' rhodium(II)-catalysed intramolecular C-H insertions

AU - Lombard, Fanny J.

AU - Lepage, Romain J.

AU - Schwartz, Brett D.

AU - Johnston, Ryne C.

AU - Healy, Peter C.

AU - Krenske, Elizabeth H.

AU - Coster, Mark J.

PY - 2018

Y1 - 2018

N2 - A tetrahydropyranyl acetal bearing a proximal phenyl diazoketone substituent underwent Rh(ii)-catalysed C-H insertion via an 'anomalous' C-O bond-forming, rather than C-C bond-forming, transformation, giving spirocyclic orthoesters. Density functional theory calculations with M06 show that the formation of these anomalous products involves hydride transfer to the rhodium carbene, giving an intermediate zwitterion which undergoes C-O bond formation in preference to C-C bond formation.

AB - A tetrahydropyranyl acetal bearing a proximal phenyl diazoketone substituent underwent Rh(ii)-catalysed C-H insertion via an 'anomalous' C-O bond-forming, rather than C-C bond-forming, transformation, giving spirocyclic orthoesters. Density functional theory calculations with M06 show that the formation of these anomalous products involves hydride transfer to the rhodium carbene, giving an intermediate zwitterion which undergoes C-O bond formation in preference to C-C bond formation.

UR - https://www.scopus.com/pages/publications/85040184403

U2 - 10.1039/c7ob02123b

DO - 10.1039/c7ob02123b

M3 - Article

SN - 1477-0520

VL - 16

SP - 256

EP - 261

JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

IS - 2

ER -

Synthesis of spirocyclic orthoesters by 'anomalous' rhodium(II)-catalysed intramolecular C-H insertions

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