Single versus double Cu(I) catalyzed [3 + 2] azide/platinum diacetylide cycloaddition reactions

Xi Yang; Sudarsan VenkatRamani; Christopher C. Beto; Trevor J. Del Castillo; Ion Ghiviriga; Khalil A. Abboud; Adam S. Veige

doi:10.1021/acs.organomet.7b00067

Single versus double Cu(I) catalyzed [3 + 2] azide/platinum diacetylide cycloaddition reactions

Xi Yang
, Sudarsan VenkatRamani
, Christopher C. Beto
, Trevor J. Del Castillo
, Ion Ghiviriga
, Khalil A. Abboud
, Adam S. Veige

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

15 Scopus citations

Abstract

This report focuses on Cu(I) catalyzed cycloaddition reactions between organic azides and the platinum diacetylide complexes trans-(PR₃)₂Pt(C≡CR′)₂ (where PR₃ = P(OEt)₃, PEt₃, PⁿBu₃, PPhMe₂, PPh₃, and PBn₃; and R′ = H, Ph, and p-PhNO₂). Pt(II)-Diacetylides supported by P(OEt)₃, PEt₃, PⁿBu₃, and PPhMe₂ react with benzyl azide to provide syn/anti isomers of double cycloaddition products. In contrast, Pt(II)-diacetylide complexes supported by PPh₃ and PBn₃ afford single cycloaddition products, exclusively. Steric congestion enforced by the larger phosphines PPh₃ and PBn₃ prevent the second cycloaddition. Ground state DFT computations provide some insight into the divergent reactivity and indicate that the π-acidity of the phosphine ligands is a variable in the single vs double cycloaddition outcome.

Original language	English (US)
Pages (from-to)	1352-1357
Number of pages	6
Journal	Organometallics
Volume	36
Issue number	7
DOIs	https://doi.org/10.1021/acs.organomet.7b00067
State	Published - Apr 10 2017
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{b6f70858e2354bea98379cf0f0829bdc,

title = "Single versus double Cu(I) catalyzed [3 + 2] azide/platinum diacetylide cycloaddition reactions",

abstract = "This report focuses on Cu(I) catalyzed cycloaddition reactions between organic azides and the platinum diacetylide complexes trans-(PR3)2Pt(C≡CR′)2 (where PR3 = P(OEt)3, PEt3, PnBu3, PPhMe2, PPh3, and PBn3; and R′ = H, Ph, and p-PhNO2). Pt(II)-Diacetylides supported by P(OEt)3, PEt3, PnBu3, and PPhMe2 react with benzyl azide to provide syn/anti isomers of double cycloaddition products. In contrast, Pt(II)-diacetylide complexes supported by PPh3 and PBn3 afford single cycloaddition products, exclusively. Steric congestion enforced by the larger phosphines PPh3 and PBn3 prevent the second cycloaddition. Ground state DFT computations provide some insight into the divergent reactivity and indicate that the π-acidity of the phosphine ligands is a variable in the single vs double cycloaddition outcome.",

author = "Xi Yang and Sudarsan VenkatRamani and Beto, \{Christopher C.\} and \{Del Castillo\}, \{Trevor J.\} and Ion Ghiviriga and Abboud, \{Khalil A.\} and Veige, \{Adam S.\}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = apr,

day = "10",

doi = "10.1021/acs.organomet.7b00067",

language = "English (US)",

volume = "36",

pages = "1352--1357",

journal = "Organometallics",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Single versus double Cu(I) catalyzed [3 + 2] azide/platinum diacetylide cycloaddition reactions

AU - Yang, Xi

AU - VenkatRamani, Sudarsan

AU - Beto, Christopher C.

AU - Del Castillo, Trevor J.

AU - Ghiviriga, Ion

AU - Abboud, Khalil A.

AU - Veige, Adam S.

PY - 2017/4/10

Y1 - 2017/4/10

N2 - This report focuses on Cu(I) catalyzed cycloaddition reactions between organic azides and the platinum diacetylide complexes trans-(PR3)2Pt(C≡CR′)2 (where PR3 = P(OEt)3, PEt3, PnBu3, PPhMe2, PPh3, and PBn3; and R′ = H, Ph, and p-PhNO2). Pt(II)-Diacetylides supported by P(OEt)3, PEt3, PnBu3, and PPhMe2 react with benzyl azide to provide syn/anti isomers of double cycloaddition products. In contrast, Pt(II)-diacetylide complexes supported by PPh3 and PBn3 afford single cycloaddition products, exclusively. Steric congestion enforced by the larger phosphines PPh3 and PBn3 prevent the second cycloaddition. Ground state DFT computations provide some insight into the divergent reactivity and indicate that the π-acidity of the phosphine ligands is a variable in the single vs double cycloaddition outcome.

AB - This report focuses on Cu(I) catalyzed cycloaddition reactions between organic azides and the platinum diacetylide complexes trans-(PR3)2Pt(C≡CR′)2 (where PR3 = P(OEt)3, PEt3, PnBu3, PPhMe2, PPh3, and PBn3; and R′ = H, Ph, and p-PhNO2). Pt(II)-Diacetylides supported by P(OEt)3, PEt3, PnBu3, and PPhMe2 react with benzyl azide to provide syn/anti isomers of double cycloaddition products. In contrast, Pt(II)-diacetylide complexes supported by PPh3 and PBn3 afford single cycloaddition products, exclusively. Steric congestion enforced by the larger phosphines PPh3 and PBn3 prevent the second cycloaddition. Ground state DFT computations provide some insight into the divergent reactivity and indicate that the π-acidity of the phosphine ligands is a variable in the single vs double cycloaddition outcome.

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U2 - 10.1021/acs.organomet.7b00067

DO - 10.1021/acs.organomet.7b00067

M3 - Article

AN - SCOPUS:85019593674

SN - 0276-7333

VL - 36

SP - 1352

EP - 1357

JO - Organometallics

JF - Organometallics

IS - 7

ER -

Single versus double Cu(I) catalyzed [3 + 2] azide/platinum diacetylide cycloaddition reactions

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