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. 2009 Feb 23;28(4):950-952.
doi: 10.1021/om801069s.

Platinum(II) Enyne Cycloisomerization Catalysis: Intermediates and Resting States

D Luke Nelsen  1 , Michel R Gagné
Affiliations

Platinum(II) Enyne Cycloisomerization Catalysis: Intermediates and Resting States

D Luke Nelsen et al. Organometallics. .

Abstract

In situ generated [(PPP)Pt][BF(4)](2) (PPP = triphos) catalyzes the cycloisomerization of 1,6-enyne-ols by initiative pi-activation of the alkyne. This generates an isolable cationic Pt-alkenyl species which subsequently participates in turnover limiting protonolysis with in situ generated acid. This latter reactivity contrasts cationic Pt-alkyls which are more difficult to protonolyze. Mechanistic studies on isolated Pt-alkenyls, and deuterium labeling helped to elucidate the mechanistic details.

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Figures

Figure 1
Figure 1
Chem3D representation of 3. BF4− anion removed for clarity. Selective bond lengths (Å): Pt-P1 = 2.283(6), Pt-P2 = 2.275(6), Pt-P3 = 2.284(6), Pt-C1 = 2.10(2), C1-C14 = 1.33(3). Selective bond angles (deg): C1-Pt-P1 = 97.6(5), C1-Pt-P3 = 93.0(5), P1-Pt-P2 = 84.4(2), P2-Pt-P3 = 85.4(2).
Scheme 1
Scheme 1
Scheme 2
Scheme 2
Scheme 3
Scheme 3
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