CaltechAUTHORS
Published June 12, 2019 | Version Accepted Version + Submitted + Supplemental Material
Journal Article Open

Vinyl Carbocations Generated under Basic Conditions and Their Intramolecular C–H Insertion Reactions

Creators

  • 1. ROR icon University of California, Los Angeles
  • 2. ROR icon University of California, Riverside

Abstract

Here we report the surprising discovery that high-energy vinyl carbocations can be generated under strongly basic conditions, and that they engage in intramolecular sp³ C–H insertion reactions through the catalysis of weakly coordinating anion salts. This approach relies on the unconventional combination of lithium hexamethyldisilazide base and the commercially available catalyst, triphenylmethylium tetrakis(pentafluorophenyl)borate. These reagents form a catalytically active lithium species that enables the application of vinyl cation C–H insertion reactions to heteroatom-containing substrates.

Additional Information

© 2019 American Chemical Society. Received 24 February 2019. Published online 13 May 2019. Published in issue 12 June 2019. Financial support for this work was generously provided by the David and Lucile Packard Foundation (to H.M.N.), the Alfred P. Sloan Foundation (to H.M.N.), the Pew Charitable Trusts (to H.M.N), the NIH-NIGMS (R35 GM128936 to H.M.N.), and the National Science Foundation (CHE-1764328 to K.N.H., CHE-1455348 to V.L., and DGE-1650604 to S.P. and B.W.). A.L.B. and B.W. thank the Christopher S. Foote Fellowship for funding. The authors thank the UCLA Molecular Instrumentation Center for NMR and mass spectroscopy instrumentation as well as the Mass Spectrometry facility at the University of California, Irvine. Computations were performed on the Hoffman2 cluster at UCLA and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the NSF (OCI-1053575). The authors declare no competing financial interest.

Attached Files

Accepted Version - nihms-1035920.pdf

Submitted - strong-bases-and-weak-anions-in-catalytic-c-h-insertion-reactions-of-vinyl-carbocations.pdf

Supplemental Material - ja9b02110_si_001.pdf

Files

ja9b02110_si_001.pdf

Files (35.7 MB)

Name Size
md5:f0dabd380e4539730c2aba8ee3cc3a33
32.6 MB Preview Download
md5:a635fb23ad7c4ec92207529ac0007f96
1.5 MB Preview Download
md5:9d4410198724a1deb9d48ad9efa958b7
1.6 MB Preview Download

Additional details

Additional titles

Alternative title
Strong Bases and Weak Anions in Catalytic C–H Insertion Reactions of Vinyl Carbocations

Identifiers

PMCID
PMC6608570
Eprint ID
110213
Resolver ID
CaltechAUTHORS:20210811-225351518

Related works

Describes
10.26434/chemrxiv.7453223.v1 (DOI)

Funding

David and Lucile Packard Foundation
Alfred P. Sloan Foundation
Pew Charitable Trust
NIH
R35 GM128936
NSF
CHE-1764328
NSF
CHE-1455348
NSF Graduate Research Fellowship
DGE-1650604
UCLA
NSF
OCI-1053575

Dates

Created
2021-08-12
Created from EPrint's datestamp field
Updated
2021-08-18
Created from EPrint's last_modified field