ChemInform Abstract: REACTION OF PHOSPHORYLATED ALLENES WITH SULFENYL CHLORIDES

Abstract

Die Allenderivate (I), (IV), (VI) und (IX) werden mit den Sulfenylderivaten (II) bzw. (VII) umgesetzt.

Bifunctionalized Allenes, Part XI: Competitive Electrophilic Cyclization and Addition Reactions of 4‐Phosphorylated Allenecarboxylates

“…In the second case (Scheme ), this reaction pathway is probably favorable from an energetic point of view. If the phosphine oxide group takes place as an internal nucleophile in the cyclization, the prepared cyclic compounds should be phosphonium salts C 1 (Scheme ), since in this case the stabilization by the elimination of phenyl halide (second stage of an Arbuzov‐type rearrangement) and formation of stable products with tetracoordinated phosphorus is impossible. Moreover, the reason for the absence of as the cyclic products as well as the adducts on the C 3 C 4 ‐double bond of the allenoate system obviously consists of the fact that the corresponding onium ions B 1 (Scheme ) is not formed in the reaction of the 4‐(diphenylphosphoryl)‐allenoates 2a–d with electrophiles.…”

Fifty Years of (Benz)oxaphospholene Chemistry

“…The terminal alkene in the 2-phosphonopentadiene 94 is activatedb yt he electrophile, whichi sf ollowed by ring closure through intramolecular attack of the phosphoryl group onto the internal double bond (Scheme 20). [80,[90][91][92][93][94] 3-Monosubstituted allenylphosphonates gave mixtures of oxaphospholenes and 1,2-and 2,3-adducts 98 and 99. In reaction with sulfenylhalides, 1,3,3-trisubstituted and 1,3-disubstituted allenylphosphonates exclusively yieldedt he oxaphospholene cyclization products 97, [80,81] while 3,3-disubstitued allenylphosphonates also gave small amountso f1 ,2-adducts 98 of the sulfenylchloridei ns ome cases.…”

“…[75,76] Not only halogen sources could initiate cyclization of allenylphosphonates 96.S ulfenyl-, [77][78][79][80][81] selenyl- [52,[82][83][84][85][86][87] or tellurylhalides [88,89] efficiently gave rise to 4-chalcogeno oxaphospholenes 97 (Scheme 21). [90][91][92] 1-Vinyl-substituted allenylphosphonates gave mixtures of phosphonylated thiophenes 100 and 4-thio oxaphospholenes 97. [78,79,81,84,85] Unsubstituteda llenylphosphonates did not produce oxaphospholenic cyclizationp roductsa nd only yielded 1,2-adducts 98 or 2,3-adducts 99.…”

“…In reaction with sulfenylhalides, 1,3,3‐trisubstituted and 1,3‐disubstituted allenylphosphonates exclusively yielded the oxaphospholene cyclization products 97 , while 3,3‐disubstitued allenylphosphonates also gave small amounts of 1,2‐adducts 98 of the sulfenylchloride in some cases . Unsubstituted allenylphosphonates did not produce oxaphospholenic cyclization products and only yielded 1,2‐adducts 98 or 2,3‐adducts 99 . 3‐Monosubstituted allenylphosphonates gave mixtures of oxaphospholenes and 1,2‐ and 2,3‐adducts 98 and 99 .…”

“…Unsubstituted allenylphosphonates did not produce oxaphospholenic cyclization products and only yielded 1,2‐adducts 98 or 2,3‐adducts 99 . 3‐Monosubstituted allenylphosphonates gave mixtures of oxaphospholenes and 1,2‐ and 2,3‐adducts 98 and 99 . 1‐Vinyl‐substituted allenylphosphonates gave mixtures of phosphonylated thiophenes 100 and 4‐thio oxaphospholenes 97 .…”