Diels‐Alder reaction of (2,4,6‐trialkylphenyl)phospholes with N‐phenylmaleimide

Abstract

2,4,6‐Trialkylphenylphospholes 3a (R=Me), 3b (R=i–Pr) and 3c (R=t–Bu), with increasing flattening at phosphorus and hence with increasing electron delocalisation, underwent the Diels‐Alder reaction with N‐phenylmaleimide to give predominantly cycloadducts 4a–c with the trialkylphenyl substituents anti to the phosphanorbornene double bond. With increasing aromaticity, the cycloaddition was slower. The stereostructure of the products (6 and 7) obtained after oxidation was confirmed by stereospecific 2JPC NMR couplings and by an independent synthesis. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:271–275, 2000

Heterobimetallic Gold/Ruthenium Complexes Synthesized via Post‐functionalization and Applied in Dual Photoredox Gold Catalysis

“…This is not surprising as the reaction of trivalent phospholes with dienophiles usually yields the anti isomer exclusively or very predominantly. [ 25 , 26 , 44 ] Nevertheless, this example shows the versatility of the applied synthetic strategy and indicates that the coordinated {Ru(bpy) 2 } moiety solitarily does not hamper the Diels‐Alder reaction. Coordination of the {AuCl} fragment to the phosphole seems to suppress the formation of the anti product and induces syn stereochemistry.…”

Heterobimetallic Gold/Ruthenium Complexes Synthesized via Post‐functionalization and Applied in Dual Photoredox Gold Catalysis

“…This is not surprising as the reaction of trivalent phospholes with dienophiles usually yields the anti isomer exclusively or very predominantly. [ 25 , 26 , 44 ] Nevertheless, this example shows the versatility of the applied synthetic strategy and indicates that the coordinated {Ru(bpy) 2 } moiety solitarily does not hamper the Diels‐Alder reaction. Coordination of the {AuCl} fragment to the phosphole seems to suppress the formation of the anti product and induces syn stereochemistry.…”

Revisiting the 7‐Phospanorbornene Family: New P‐Alkyl Derivatives

“…The dimerization of two molecules of a phosphole oxide is completely regio‐ and stereoselective, which was justified by semiempirical calculations . The results of Quin, Mathey, and other authors revealed the importance of the 7‐phosphanorbornene derivatives in fragmentation‐related phosphorylation reactions , complexations , and in re‐functionalizations including deoxygenations . The Bayer–Villiger oxidation of 7‐phosphanorbornenes leads to valuable oxaphosphabicyclo[2.2.2]octene derivatives that may be useful in fragmentation‐related phosphorylations .…”

Study on the uv light-mediated fragmentation of 7-(2,4,6-trialkylphenyl-)7-phosphanorbornene 7-oxides in alcohols: New evidences on the mechanism

“…Chemical shifts are downfield relative to 85% H 3 PO 4 . Gas chro- 1, 10, and 11) were prepared by the trapping of phosphole oxides as described earlier [6][7][8]. The phosphanorbornenes with anti aryl group to the double bond (4 and 5) were synthesized by the trapping of phospholes followed by oxidation at the phosphorus atom [8].…”

Heterobimetallic Gold/Ruthenium Complexes Synthesized via Post‐functionalization and Applied in Dual Photoredox Gold Catalysis

“…This is not surprising as the reaction of trivalent phospholes with dienophiles usually yields the anti isomer exclusively or very predominantly. [ 25 , 26 , 44 ] Nevertheless, this example shows the versatility of the applied synthetic strategy and indicates that the coordinated {Ru(bpy) 2 } moiety solitarily does not hamper the Diels‐Alder reaction. Coordination of the {AuCl} fragment to the phosphole seems to suppress the formation of the anti product and induces syn stereochemistry.…”

Revisiting the 7‐Phospanorbornene Family: New P‐Alkyl Derivatives

“…The dimerization of two molecules of a phosphole oxide is completely regio‐ and stereoselective, which was justified by semiempirical calculations . The results of Quin, Mathey, and other authors revealed the importance of the 7‐phosphanorbornene derivatives in fragmentation‐related phosphorylation reactions , complexations , and in re‐functionalizations including deoxygenations . The Bayer–Villiger oxidation of 7‐phosphanorbornenes leads to valuable oxaphosphabicyclo[2.2.2]octene derivatives that may be useful in fragmentation‐related phosphorylations .…”

Study on the uv light-mediated fragmentation of 7-(2,4,6-trialkylphenyl-)7-phosphanorbornene 7-oxides in alcohols: New evidences on the mechanism

“…Chemical shifts are downfield relative to 85% H 3 PO 4 . Gas chro- 1, 10, and 11) were prepared by the trapping of phosphole oxides as described earlier [6][7][8]. The phosphanorbornenes with anti aryl group to the double bond (4 and 5) were synthesized by the trapping of phospholes followed by oxidation at the phosphorus atom [8].…”

Heterobimetallic Gold/Ruthenium Complexes Synthesized via Post‐functionalization and Applied in Dual Photoredox Gold Catalysis

“…This is not surprising as the reaction of trivalent phospholes with dienophiles usually yields the anti isomer exclusively or very predominantly. [ 25 , 26 , 44 ] Nevertheless, this example shows the versatility of the applied synthetic strategy and indicates that the coordinated {Ru(bpy) 2 } moiety solitarily does not hamper the Diels‐Alder reaction. Coordination of the {AuCl} fragment to the phosphole seems to suppress the formation of the anti product and induces syn stereochemistry.…”

Revisiting the 7‐Phospanorbornene Family: New P‐Alkyl Derivatives

“…The dimerization of two molecules of a phosphole oxide is completely regio‐ and stereoselective, which was justified by semiempirical calculations . The results of Quin, Mathey, and other authors revealed the importance of the 7‐phosphanorbornene derivatives in fragmentation‐related phosphorylation reactions , complexations , and in re‐functionalizations including deoxygenations . The Bayer–Villiger oxidation of 7‐phosphanorbornenes leads to valuable oxaphosphabicyclo[2.2.2]octene derivatives that may be useful in fragmentation‐related phosphorylations .…”

Study on the uv light-mediated fragmentation of 7-(2,4,6-trialkylphenyl-)7-phosphanorbornene 7-oxides in alcohols: New evidences on the mechanism

“…Chemical shifts are downfield relative to 85% H 3 PO 4 . Gas chro- 1, 10, and 11) were prepared by the trapping of phosphole oxides as described earlier [6][7][8]. The phosphanorbornenes with anti aryl group to the double bond (4 and 5) were synthesized by the trapping of phospholes followed by oxidation at the phosphorus atom [8].…”