Synthesis of odorants in flow and their applications in perfumery

• Merlin Kleoff,
• Paul Kiler and
• Philipp Heretsch

Beilstein J. Org. Chem. 2022, 18, 754–768, doi:10.3762/bjoc.18.76

• achieved within milliseconds initializing bromine–lithium exchange of bromochloromethane to generate (chloromethyl)lithium. This carbenoid species readily reacts with terpenyl pinacol boronates 17, resulting in the formation of intermediate 18, which undergoes 1,2-anionotropic rearrangement to the

Thiophene-forming one-pot synthesis of three thienyl-bridged oligophenothiazines and their electronic properties

• Dominik Urselmann,
• Konstantin Deilhof,
• Bernhard Mayer and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2016, 12, 2055–2064, doi:10.3762/bjoc.12.194

• our one-pot bromine-lithium-exchange-borylation-Suzuki (BLEBS) sequence [78], employing an excess of 3,7-dibromo-10-hexyl-10H-phenothiazine (3) [45] as a coupling component in the Suzuki step (Scheme 1). With three bromo-substituted (oligo)phenothiazines 1 in hand the consecutive pseudo five-component

• oligophenothiazines 3 (calculated with the B3LYP functional in vacuo and the 6-311G(d,p) basis set). One-pot bromine-lithium-exchange-borylation-Suzuki (BLEBS) synthesis of 7-bromo-substituted phenothiazines 1b and 1c with 3,7-dibromo-10-hexyl-10H-phenothiazine (2). Pseudo five-component Sonogashira-Glaser

SmI₂-mediated dimerization of indolylbutenones and synthesis of the myxobacterial natural product indiacen B

• Nils Marsch,
• Peter G. Jones and
• Thomas Lindel

Beilstein J. Org. Chem. 2015, 11, 1700–1706, doi:10.3762/bjoc.11.184

• functionalized the indole 6-position. Verticillatine B (20) was synthesized in a short sequence from commercially available 5-bromoindole (19) via halogen–metal exchange (Scheme 4). The indole nitrogen was first protected with a TBS group, followed by bromine–lithium exchange with tert-butyllithium [35]. The

Gold(I)-catalyzed 6-endo hydroxycyclization of 7-substituted-1,6-enynes

• Ana M. Sanjuán,
• Alberto Martínez,
• Patricia García-García,
• Manuel A. Fernández-Rodríguez and
• Roberto Sanz

Beilstein J. Org. Chem. 2013, 9, 2242–2249, doi:10.3762/bjoc.9.263

• ]. Alternatively, several o-(alkynyl)bromobenzenes [34] could be transformed into the corresponding derivatives 1 by bromine–lithium exchange and further treatment with 3,3-dimethylallyl bromide in the presence of TMEDA [23]. We selected 1-(2-(2-(3-methylbut-2-enyl)phenyl)ethynyl)benzene (1a) as model substrate

An approach towards azafuranomycin analogs by gold-catalyzed cycloisomerization of allenes: synthesis of (αS,2R)-(2,5-dihydro-1H-pyrrol-2-yl)glycine

• Jörg Erdsack and
• Norbert Krause

Beilstein J. Org. Chem. 2013, 9, 1936–1942, doi:10.3762/bjoc.9.229

• desired dehalogenated dihydropyrrole with 66% yield (formula not shown). For the conversion of 19 to 20, we applied a bromine–lithium exchange with 2 equivalents of t-BuLi in diethyl ether at –90 °C [71], followed by hydrolysis. Even though oxazolidines are known to be sensitive towards organolithium

Stereoselective synthesis of tetrasubstituted alkenes via a sequential carbocupration and a new sulfur–lithium exchange

• Andreas Unsinn,
• Cora Dunst and
• Paul Knochel

Beilstein J. Org. Chem. 2012, 8, 2202–2206, doi:10.3762/bjoc.8.248

• these reactions are often complicated by radical side reactions [20][21]. This new, direct sulfur–lithium exchange on an alkenyl thioether of type 4 involves the use of a bromobiphenyl R-group, which by treatment with BuLi at low temperatures, undergoes first a fast bromine–lithium exchange leading to

• starting from 2,2’-dibromobiphenyl. Thus, the performance of a double bromine–lithium exchange with BuLi (1.1 equiv, −78 °C, 0.25 h) followed by a quenching with tetramethylthiuram disulfide (1.1 equiv, −78 to 25 °C, 12 h) furnishes the dithiocarbamate 13 in 82% yield. Since the reduction to the free thiol

Directed aromatic functionalization in natural-product synthesis: Fredericamycin A, nothapodytine B, and topopyrones B and D

• Charles Dylan Turner and
• Marco A. Ciufolini

Beilstein J. Org. Chem. 2011, 7, 1475–1485, doi:10.3762/bjoc.7.171

• benzamide 56 with sec-BuLi/TMEDA (1.05 equiv, 3 h, −78 °C) and addition of the resulting organolithium agent to 65 was presumed to form the alkoxide 66. In situ treatment of 66 with t-BuLi induced bromine–lithium exchange and cyclization of organolithium species 67 to a product that was believed to be 68

Bromine–lithium exchange: An efficient tool in the modular construction of biaryl ligands

• Laurence Bonnafoux,
• Frédéric R. Leroux and
• Françoise Colobert

Beilstein J. Org. Chem. 2011, 7, 1278–1287, doi:10.3762/bjoc.7.148

• Laurence Bonnafoux Frederic R. Leroux Francoise Colobert Laboratoire de stéréochimie, UMR 7509, CNRS-Université de Strasbourg, ECPM, 25 rue Becquerel, F-67087 Strasbourg Cedex 02, France 10.3762/bjoc.7.148 Abstract Regioselective bromine–lithium exchange reactions on polybrominated biaryls enable

• analogues. So far, such a process, based on the effective discrimination between bromine atoms as a function of their chemical environment, has been observed only sporadically. Keywords: biaryl; bromine–lithium exchange; ligand; lithiation; phosphine; Introduction Atropisomeric biaryls are important

• -, tri-, and even tetra-substituted ortho,ortho'-dibromobiphenyls [25][28][31][36][37][38]. These have the advantage that, by means of successive or simultaneous bromine–lithium exchanges, a huge panel of substituents can be introduced into the biphenyl backbone. The bromine–lithium exchange reaction is

Homocoupling of aryl halides in flow: Space integration of lithiation and FeCl₃ promoted homocoupling

• Aiichiro Nagaki,
• Yuki Uesugi,
• Yutaka Tomida and
• Jun-ichi Yoshida

Beilstein J. Org. Chem. 2011, 7, 1064–1069, doi:10.3762/bjoc.7.122

• –lithium exchange reaction. Methanol (neat, flow rate: 3.0 mL/min) was added in M2 ( = 500 μm) and the mixture was passed through R2 ( = 1000 μm, L = 50 cm) to protonate p-methoxyphenyllithium. The reactions were carried out with varying residence time in R1 (tR1: 0.2–6.3 s) and varying temperature (T: −78

• R2) shown in Figure 1, was used. A solution of p-bromoanisole (Ar–X) (0.10 M in THF, flow rate: 6.0 mL/min) and a solution of n-butyllithium (0.40 M in hexane, flow rate: 1.5 mL/min) were introduced to M1 ( = 250 μm) by syringe pumps. The resulting mixture was passed through R1 to conduct the bromine

Synthesis, electronic properties and self-assembly on Au{111} of thiolated (oligo)phenothiazines

• Adam W. Franz,
• Svetlana Stoycheva,
• Michael Himmelhaus and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2010, 6, No. 72, doi:10.3762/bjoc.6.72

• “alligator-clips” and their electronic properties as studied by cyclic voltammetry (CV), spectroscopic and spectrometric methods. Furthermore, their chemisorption and SAM formation on Au{111} were studied by ellipsometry. Results and Discussion Synthesis The facile bromine–lithium exchange of bromo

• accomplished according to a standard protocol [18]. Thus, solutions of bromo phenothiazines 1 [32][52] were cooled to −78 °C and reacted with n-BuLi (1a and 1b) or t-BuLi (1c–e and 3), respectively, to give the corresponding lithio phenothiazines via bromine–lithium exchange. Subsequent addition of elemental

Trifluoromethyl ethers – synthesis and properties of an unusual substituent

• Frédéric R. Leroux,
• Baptiste Manteau,
• Jean-Pierre Vors and
• Sergiy Pazenok

Beilstein J. Org. Chem. 2008, 4, No. 13, doi:10.3762/bjoc.4.13

• benzene. Synthesis and Nitration of N-Acetyl-(trifluoromethoxy)anilines. Bromine/lithium exchange of bromo(trifluoromethoxy)benzenes. Metalation of (trifluoromethoxy)benzene. Metalation of (trifluoromethoxy)naphthalenes. Competition between -CF3- and -OCF3 in Metalation reactions. Competition between -F