INVESTIGADORES
REY Valentina
congresos y reuniones científicas
Título:
Competitive reaction pathways for o-amidoaryl radicals: 1,5 or 1,6 hydrogen transfer versus nuchleophilic
Autor/es:
REY, VALENTINA; PEÑÉÑORY, ALICIA B
Lugar:
Los Cocos,Córdoba, Argentina
Reunión:
Conferencia; 9° Conferencia Latinoamericana de Fisico Química Orgánica (CLAFQO); 2007
Institución organizadora:
CLAFQO
Resumen:
We have described for the first time the reactivity of sulfur-centered nucleophiles such as
thiourea anion (1, -SCNH(NH2)),1 and thioacetate anion (2, MeCOS-)2 in photoinduced aromatic
radical nucleophilic substitution as a one-pot method for the synthesis of several sulfur aromatic
compounds from moderate to good yields. This reaction provides a very good alternative to
introduce a sulfur functionality in aryl compounds by ipso substitution of an adequate leaving group.
To apply this methodology to the synthesis of benzotiazoles, we have studied the reactivity
of o-iodoanilides (3) with anions 1 and 2 in photoinduced reactions in DMSO, as a strategy to
replace the iodide by a sulfur anion. Further reaction of this anion with the carbonyl group would
render the desired heterocycle. These reactions proceed with an initial photoinduced electron
transfer (PET) from 1 to the iodide 3, followed by fragmentation of the corresponding radical anion to
finally afford the o-amidoaryl radical 4. The latter radical have three competitive reaction pathways
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
finally afford the o-amidoaryl radical 4. The latter radical have three competitive reaction pathways
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
replace the iodide by a sulfur anion. Further reaction of this anion with the carbonyl group would
render the desired heterocycle. These reactions proceed with an initial photoinduced electron
transfer (PET) from 1 to the iodide 3, followed by fragmentation of the corresponding radical anion to
finally afford the o-amidoaryl radical 4. The latter radical have three competitive reaction pathways
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
finally afford the o-amidoaryl radical 4. The latter radical have three competitive reaction pathways
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
radical nucleophilic substitution as a one-pot method for the synthesis of several sulfur aromatic
compounds from moderate to good yields. This reaction provides a very good alternative to
introduce a sulfur functionality in aryl compounds by ipso substitution of an adequate leaving group.
To apply this methodology to the synthesis of benzotiazoles, we have studied the reactivity
of o-iodoanilides (3) with anions 1 and 2 in photoinduced reactions in DMSO, as a strategy to
replace the iodide by a sulfur anion. Further reaction of this anion with the carbonyl group would
render the desired heterocycle. These reactions proceed with an initial photoinduced electron
transfer (PET) from 1 to the iodide 3, followed by fragmentation of the corresponding radical anion to
finally afford the o-amidoaryl radical 4. The latter radical have three competitive reaction pathways
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
finally afford the o-amidoaryl radical 4. The latter radical have three competitive reaction pathways
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
replace the iodide by a sulfur anion. Further reaction of this anion with the carbonyl group would
render the desired heterocycle. These reactions proceed with an initial photoinduced electron
transfer (PET) from 1 to the iodide 3, followed by fragmentation of the corresponding radical anion to
finally afford the o-amidoaryl radical 4. The latter radical have three competitive reaction pathways
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
finally afford the o-amidoaryl radical 4. The latter radical have three competitive reaction pathways
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
1, -SCNH(NH2)),1 and thioacetate anion (2, MeCOS-)2 in photoinduced aromatic
radical nucleophilic substitution as a one-pot method for the synthesis of several sulfur aromatic
compounds from moderate to good yields. This reaction provides a very good alternative to
introduce a sulfur functionality in aryl compounds by ipso substitution of an adequate leaving group.
To apply this methodology to the synthesis of benzotiazoles, we have studied the reactivity
of o-iodoanilides (3) with anions 1 and 2 in photoinduced reactions in DMSO, as a strategy to
replace the iodide by a sulfur anion. Further reaction of this anion with the carbonyl group would
render the desired heterocycle. These reactions proceed with an initial photoinduced electron
transfer (PET) from 1 to the iodide 3, followed by fragmentation of the corresponding radical anion to
finally afford the o-amidoaryl radical 4. The latter radical have three competitive reaction pathways
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
finally afford the o-amidoaryl radical 4. The latter radical have three competitive reaction pathways
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
depending on the structure of the a-carbonyl moiety (Scheme 1): a) R = CH3, coupling with 1 to
render the thiolate anion 5; b) R = t-Bu, 1,6-hydrogen transfer, followed by a 1,4-aryl migration to
afford an amidyl radical (6); and c) 1,5-hydrogen transfer to give a a-carbonyl radical (7). Evidences
for the proposed mechanism will be discussed.
for the proposed mechanism will be discussed.
afford an amidyl radical (