- Thermal and photochemical decomposition of N- [2-( 3,3-Dimethyl-1-butynyl)-2,5,5-trimethyl-1-pyrrolidinyl] nitrene
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Oxidation of N-aminopyrrolidine 5 with tert-butyl hypochlorite at -130 °C yields the 1,1-disubstituted diazene 4, which is stable in dimethyl ether solution at this temperature. Thermal (-90 °C) or photochemical (-130 deg;C, λ > 330 nm) decomposition of 4 furnishes singlet alkyl propargyl biradical 1, which undergoes fragmentation to 16, cyclization to 17, and disproportionate to 18 and 19 (Table I). The absence of products attributable to the cyclization of 1 to vinyl carbene 2 (cf. eq 1) is interpreted as evidence that cyclization according to eq 1, when observed, occurs directly from the triplet biradical in competition with intersystem crossing.
- Horner,Rudolph,Wolff, Steven,Agosta, William C.
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- On the Mechanism of the Metal Mediated Vinylic Cross Coupling Reactions. 2. Reductive Elimination: Preparation, Molecular Structure, and Thermal Chemistry of (?-Alkynyl)(?-vinyl)platinum(II) Complexes
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Reaction of RCCLi with CH2=C(CH3)Pt(PPh3)2(OTf) results in cis- and trans-(?-alkynyl)(?-vinyl)platinum(II) complexes.The cis isomer is the kinetic product and the trans one the thermodynamic one.X-ray crystal structures of both the cis and trans isomer
- Stang, Peter J.,Kowalski, Mark H.
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- Organoboranes. 38. A Facile and Highly Efficient Addition of B-1-Alkynyl-9-borabicyclononanes to Aldehydes and Ketones: An Exceptionally Chemoselective Synthesis of Propargylic Alcohols
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B-1-Alkynyl-9-borabicyclononanes (B-1-alkynyl-9-BBN) readily undergo addition to aldehydes and ketones and afford the propargylic alcohols in very high isolated yields.Unlike many other alkynyl metals (RCCM, M = Li, Na, K, Mg, Zn, and Al), which
- Brown, Herbert C.,Molander, Gary A.,Singh, Shankar M.,Racherla, Uday S.
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p. 1577 - 1582
(2007/10/02)
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