Introduction 7108 2. Reaction of Indoles with Nitroalkenes 7109 2.1. Uncatalyzed FC Reactions 7109 2.2. Brønsted Acid Catalyzed FC Reactions 7110 2.3. Lewis Acid Catalyzed FC Reactions 7112 2.4. Organocatalyzed FC Reactions 7117 2.5. FC Reactions Included in Tandem, Cascade, and One-Pot Processes 7119 2.6. Base Promoted Conjugate Additions of Indoles to Nitroalkenes 7123 3. Reaction of Indolenine Derivatives 7124 3.1. Reaction of Nitroalkanes with Gramines 7124 3.2. Reaction of Nitroalkanes with Sulfonyl Indoles 7124 3.3. Reaction of Nitroalkanes with Other Derivatives 7126 4. Nitroaldol Reaction on Indolyl-3-carbaldehydes 7126 5. Direct Synthesis of Nitro Indoles by the Fischer Reaction 7129 6. Synthetic Applications of Nitro Indoles 7129 6.1. Synthesis of Tryptophans 7129 6.2. Synthesis of Polycyclic Compounds 7130 6.2.1. Ergot Alkaloids and Related Derivatives 7130 6.2.2. Other Polycyclic Compounds 7132 6.3. Synthesis of β-Carbolines 7135 6.4. Synthesis of Other Tryptamine Derivatives 7141 7. Conclusion 7143 Author Information 7143 Corresponding Author 7143 Notes 7143 Biographies 7143 Acknowledgments 7144 Abbreviations 7144 References 7144

The chlorination of readily available secondary and tertiary alkyl phenyl sulfides using (dichloroiodo)benzene (PhICl) is reported. This mild and rapid nucleophilic chlorination is extended to sulfa-Michael derived sulfides, affording elimination-sensitive β-chloro carbonyl and nitro compounds in good yields. The chlorination of enantioenriched benzylic sulfides to the corresponding inverted chlorides proceeds with high stereospecificity, thus providing a formal entry into enantioenriched chloro-Michael adducts. A mechanism implying the formation of a dichloro-λ-sulfurane intermediate is proposed.

A three‐component coupling of two different benzazole compounds with p‐toluenesulfinic acid allows the efficient preparation of unsymmetrical arylsulfonyl bisbenzazole derivatives. Substitution of the arylsulfonyl group from these adducts using sodium borohydride leads to the corresponding bisbenzazoles. Functional implementation of the bisbenzazole system can be achieved using Grignard and Reformatsky reagents.

The new potentially N(4)-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe(II), Ni(II), Zn(II), Cu(II), Pd(II), and V(III) centers has been studied. Reaction of (1) with Fe(BF(4))(2) x 6 H(2)O yields [Fe(TpmPy)(2)](BF(4))(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn(II) or Ni(II) chlorides give the corresponding metal complexes with general formula [MCl(2)(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)]Cl(2) (5)) or the pyridyl-side (for [ZnCl(2)(TpmPy)(2)] (4), [ZnCl(2)(TpmPy(Ph))(2)] (6) and [NiCl(2)(TpmPy(Ph))(2)] (7)). The reaction of (1) with VCl(3) gives [VOCl(2)(TpmPy)] (8) that shows the N(3)-pyrazolyl coordination-mode. Moreover, (1) and (2) react with cis-[PdCl(2)(CH(3)CN)(2)] to give the disubstituted complexes [PdCl(2)(TpmPy)(2)] (9) and [PdCl(2)(TpmPy(Ph))(2)] (10), respectively, bearing the scorpionate coordinated via the pyridyl group. Compounds (9) and (10) react with Fe(BF(4))(2) to give the heterobimetallic Pd/Fe systems [PdCl(2)(mu-TpmPy)(2)Fe](BF(4))(2) (11) and [PdCl(2)(mu-TpmPy(Ph))(2)Fe(2)(H(2)O)(6)](BF(4))(4) (13), respectively. Compound (11) can also be formed from reaction of (3) with cis-[PdCl(2)(CH(3)CN)(2)], while reaction of (3) with Cu(NO(3))(2) x 2.5 H(2)O generates [Fe(mu-TpmPy)(2)Cu(NO(3))(2)](BF(4))(2) (12), confirming the multidentate ability of the new chelating ligands. The X-ray diffraction analyses of compounds (1), (3), (4), (5), and (9) are also reported.

The reaction of allylzinc bromides with α‐acryloylamidoalkyl sulfones represents a mild and straightforward entry to the corresponding homoallylamines. These dienyl compounds successfully proceeded in a ring‐closing metathesis reaction by treatment with Grubbs II catalyst to lead to 6‐alkyltetrahydropyridin‐2‐ones. Homoallylamino derivatives that contain a branched terminal alkene moiety preferentially proceeded in cross‐metathesis reaction to give the selective formation of N‐substituted fumaramides.