4045-30-1Relevant articles and documents
C-H/C-C Functionalization Approach to N-Fused Heterocycles from Saturated Azacycles
Ham, Jin Su,Park, Bohyun,Son, Mina,Roque, Jose B.,Jurczyk, Justin,Yeung, Charles S.,Baik, Mu-Hyun,Sarpong, Richmond
supporting information, p. 13041 - 13050 (2020/09/01)
Herein we report the synthesis of substituted indolizidines and related N-fused bicycles from simple saturated cyclic amines through sequential C-H and C-C bond functionalizations. Inspired by the Norrish-Yang Type II reaction, C-H functionalization of azacycles is achieved by forming α-hydroxy-β-lactams from precursor α-ketoamide derivatives under mild, visible light conditions. Selective cleavage of the distal C(sp2)-C(sp3) bond in α-hydroxy-β-lactams using a Rh-complex leads to α-acyl intermediates which undergo sequential Rh-catalyzed decarbonylation, 1,4-addition to an electrophile, and aldol cyclization, to afford N-fused bicycles including indolizidines. Computational studies provide mechanistic insight into the observed positional selectivity of C-C cleavage, which depends strongly on the groups bound to Rh trans to the phosphine ligand.
PHARMACEUTICAL COMPOUNDS
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Page/Page column 126, (2010/11/25)
The invention provides a compound of the formula (I) or a salt, solvate, tautomer or N-oxide thereof; wherein A is a saturated hydrocarbon linker group; E is a monocyclic or bicyclic carbocyclic or heterocyclic group; L1 is a bond or a linker selected from C1-C4 alkenylene, C1-C4 alkynylene, -CONR’, -NR’CO, -S, -C(O)-, -C(NR11)-, -C(S)-, -N(R11)2, C(=CHR11), -SO- and -SO2-; or L1 together with t R16 forms and 8-12 membered fused bicyclic heteroaryl ring system; L3 is a bond or a linker selected from CONH and HNCO; provided that L1 and L3 cannot both be linkers simultaneously; and provided also that L1 and L3 cannot both be a bond simultaneously; R16 is an optionally substituted 5- to 12-membered monocyclic or bicyclic carbocyclic or heterocyclic ring; L2 is absent or is a linker selected from C]-C4 alkylene, Ci-C4 alkenylene, Ci-C4 alkynylene, -CONR’-, -NR’CO-, -O-, -S-, -C(O)-, C(=CHR11), C(S)-, -N(R11)2, C3-4 cycloalkanediyl, -SO- and -SO2-; R17 is absent or is C1-6 alkyl or an optionally substituted 5 to 12 membered carbocyclic or heterocyclic ring; provided that when R17 is absent, then L2 is also absent; and R2, R3, R4, R5, R11 and R’ are as defined in the claims.
Rate Increase in Consecutive Nucleophilic Aromatic Substitution Reactions of Trichlorotrinitrobenzene: The Synthesis of 1-(Alkylamino)-3,5-dichloro-2,4,6-trinitrobenzenes
Wolff, J. Jens,Zietsch, Andreas,Oeser, Thomas,Bolocan, Ion
, p. 5164 - 5168 (2007/10/03)
The title compounds are formed by the nucleophilic aromatic substitution reaction between symtrichlorotrinitrobenzene and amines. The yields and relative rates of formation depend critically on the degree of alkylation of the nucleophile. Contrary to the usual behavior, the introduction of a second and third donor is facilitated in the case of ammonia and monoalkylamines, while this is not the case for secondary amines. This behavior is rationalized on the basis of intramolecular hydrogen bonding and substantiated by an X-ray analysis of 3,5-dichloro-2,4,6-trinitroaniline.
