Synthesis of 2-Mono- and 2,3-Disubstituted Polycyclic Alkenes

Abstract

A range of mono-and disubstituted (−Br, −Cl, −SPh, −SO 2 Ph) polycyclic alkenes has been prepared starting from alkenes by inexpensive and high-yielding synthetic routes.

An efficient protocol for the synthesis of brominated norbornene, norbornadiene,and benzonorbornadiene

“…15 To obtain monobromides 2, 14,16 5, 15−17 and 8, 16,18 n -BuLi was added to a solution of the alkene and t -BuOK in THF, followed by trapping with DBTCE. In a further step, to deprotonate monobromides, LDA was added to a solution of monobromide in THF and the solution was treated with DBTCE to give dibromides 3, 14,16 6, [15][16][17]19 and 9 16 (Scheme 1). To deprotonate the alkenes (Scheme 2), in the first step, n -butyl lithium was slowly added to a solution of alkenes and potassium tert-butoxide in THF to give a yellow solution of the potassium coordinated bicyclic alkenes 10.…”

An efficient protocol for the synthesis of brominated norbornene, norbornadiene,and benzonorbornadiene

“…15 To obtain monobromides 2, 14,16 5, 15−17 and 8, 16,18 n -BuLi was added to a solution of the alkene and t -BuOK in THF, followed by trapping with DBTCE. In a further step, to deprotonate monobromides, LDA was added to a solution of monobromide in THF and the solution was treated with DBTCE to give dibromides 3, 14,16 6, [15][16][17]19 and 9 16 (Scheme 1). To deprotonate the alkenes (Scheme 2), in the first step, n -butyl lithium was slowly added to a solution of alkenes and potassium tert-butoxide in THF to give a yellow solution of the potassium coordinated bicyclic alkenes 10.…”

The Role of Chirality in Directing the Formation of Cup‐Shaped Porphyrins and the Coordination Characteristics of such Hosts

“…[48] Benzonorbornadiene 2 was made on multigram scale in the cycloaddition of cyclopentadiene and 1,2-dibromobenzene. The stereospecific (anti) addition of benzenesulfenyl chloride (PhSCl) to 2 gave exo-(phenylthio) compound 3 rac , [49] which upon elimination (tBuOK) and then oxidation of 4 rac with MCPBA afforded a,b-unsaturated sulfone 5 rac . The treatment of 5 rac with ethyl isocyanoacetate, in the presence of tBuOK (the Barton-Zard reaction), led to the formation of pyrrole derivative 6 rac .…”

In Situ Formation of RSCl/ArSeCl and Their Application to the Synthesis of 4-Chalcogenylisocumarins/Pyrones from o-(1-Alkynyl)benzoates and (Z)-2-Alken-4-ynoates

“…Organosulfenyl chlorides or selenenyl chlorides are versatile reagents in organic synthesis. They are commonly used to install a chalcogenyl group into various organic substrates, which can be further derivatized. − In addition, they have also been widely employed to conduct a large range of synthetic transformations. − Because of the significant usefulness of these compounds, many methods for their synthesis have been reported. − Among these approaches, the most general methods include passing chlorine gas directly through a solution of thiophenol or disulfide/diselenide, reacting diphenyl disulfide/diselenide with sulfuryl chloride, ,, and chlorinating thiophenol with NCS. ,, It is noteworthy that on many occasions, rather than preparing these organochalcogenyl chloride reagents in advance, protocols utilize in situ formation of such reactive reagents, for example, from the reaction of the corresponding thiol and N -chlorosuccinimide (NCS) ,, or disulfide/diselenide and SO 2 Cl 2 …”

An efficient protocol for the synthesis of brominated norbornene, norbornadiene,and benzonorbornadiene

“…15 To obtain monobromides 2, 14,16 5, 15−17 and 8, 16,18 n -BuLi was added to a solution of the alkene and t -BuOK in THF, followed by trapping with DBTCE. In a further step, to deprotonate monobromides, LDA was added to a solution of monobromide in THF and the solution was treated with DBTCE to give dibromides 3, 14,16 6, [15][16][17]19 and 9 16 (Scheme 1). To deprotonate the alkenes (Scheme 2), in the first step, n -butyl lithium was slowly added to a solution of alkenes and potassium tert-butoxide in THF to give a yellow solution of the potassium coordinated bicyclic alkenes 10.…”

The Role of Chirality in Directing the Formation of Cup‐Shaped Porphyrins and the Coordination Characteristics of such Hosts

“…[48] Benzonorbornadiene 2 was made on multigram scale in the cycloaddition of cyclopentadiene and 1,2-dibromobenzene. The stereospecific (anti) addition of benzenesulfenyl chloride (PhSCl) to 2 gave exo-(phenylthio) compound 3 rac , [49] which upon elimination (tBuOK) and then oxidation of 4 rac with MCPBA afforded a,b-unsaturated sulfone 5 rac . The treatment of 5 rac with ethyl isocyanoacetate, in the presence of tBuOK (the Barton-Zard reaction), led to the formation of pyrrole derivative 6 rac .…”

In Situ Formation of RSCl/ArSeCl and Their Application to the Synthesis of 4-Chalcogenylisocumarins/Pyrones from o-(1-Alkynyl)benzoates and (Z)-2-Alken-4-ynoates

“…Organosulfenyl chlorides or selenenyl chlorides are versatile reagents in organic synthesis. They are commonly used to install a chalcogenyl group into various organic substrates, which can be further derivatized. − In addition, they have also been widely employed to conduct a large range of synthetic transformations. − Because of the significant usefulness of these compounds, many methods for their synthesis have been reported. − Among these approaches, the most general methods include passing chlorine gas directly through a solution of thiophenol or disulfide/diselenide, reacting diphenyl disulfide/diselenide with sulfuryl chloride, ,, and chlorinating thiophenol with NCS. ,, It is noteworthy that on many occasions, rather than preparing these organochalcogenyl chloride reagents in advance, protocols utilize in situ formation of such reactive reagents, for example, from the reaction of the corresponding thiol and N -chlorosuccinimide (NCS) ,, or disulfide/diselenide and SO 2 Cl 2 …”

An efficient protocol for the synthesis of brominated norbornene, norbornadiene,and benzonorbornadiene

“…15 To obtain monobromides 2, 14,16 5, 15−17 and 8, 16,18 n -BuLi was added to a solution of the alkene and t -BuOK in THF, followed by trapping with DBTCE. In a further step, to deprotonate monobromides, LDA was added to a solution of monobromide in THF and the solution was treated with DBTCE to give dibromides 3, 14,16 6, [15][16][17]19 and 9 16 (Scheme 1). To deprotonate the alkenes (Scheme 2), in the first step, n -butyl lithium was slowly added to a solution of alkenes and potassium tert-butoxide in THF to give a yellow solution of the potassium coordinated bicyclic alkenes 10.…”

The Role of Chirality in Directing the Formation of Cup‐Shaped Porphyrins and the Coordination Characteristics of such Hosts

“…[48] Benzonorbornadiene 2 was made on multigram scale in the cycloaddition of cyclopentadiene and 1,2-dibromobenzene. The stereospecific (anti) addition of benzenesulfenyl chloride (PhSCl) to 2 gave exo-(phenylthio) compound 3 rac , [49] which upon elimination (tBuOK) and then oxidation of 4 rac with MCPBA afforded a,b-unsaturated sulfone 5 rac . The treatment of 5 rac with ethyl isocyanoacetate, in the presence of tBuOK (the Barton-Zard reaction), led to the formation of pyrrole derivative 6 rac .…”

In Situ Formation of RSCl/ArSeCl and Their Application to the Synthesis of 4-Chalcogenylisocumarins/Pyrones from o-(1-Alkynyl)benzoates and (Z)-2-Alken-4-ynoates

“…Organosulfenyl chlorides or selenenyl chlorides are versatile reagents in organic synthesis. They are commonly used to install a chalcogenyl group into various organic substrates, which can be further derivatized. − In addition, they have also been widely employed to conduct a large range of synthetic transformations. − Because of the significant usefulness of these compounds, many methods for their synthesis have been reported. − Among these approaches, the most general methods include passing chlorine gas directly through a solution of thiophenol or disulfide/diselenide, reacting diphenyl disulfide/diselenide with sulfuryl chloride, ,, and chlorinating thiophenol with NCS. ,, It is noteworthy that on many occasions, rather than preparing these organochalcogenyl chloride reagents in advance, protocols utilize in situ formation of such reactive reagents, for example, from the reaction of the corresponding thiol and N -chlorosuccinimide (NCS) ,, or disulfide/diselenide and SO 2 Cl 2 …”