125660-37-9

Upstream product

• 76685-16-0 ethyl 2-(phenylthio)propanoate 
• 108-98-5 thiophenol 

Downstream Products

• 267668-19-9 (E)-(R)-3-methoxycarbonyl-1-methyl-2-butenyl phenyl sulfide 
• 267668-20-2 (E)-(R)-4-hydroxy-1-methyl-2-butenyl phenyl sulfide 
• 267668-21-3 (E)-(R)-4-bromo-1-methyl-2-butenyl phenyl sulfide 
• 125713-06-6 (4S,5R,8R,9R)-5-Methoxymethoxy-2-phenyl-8-((R)-1-phenylsulfanyl-ethyl)-5,8-dihydro-[1,2,4]triazolo[1,2-a]pyridazine-1,3-dione 
• 125660-43-7 (4R,5S,8S,9S)-5-Methoxymethoxy-2-phenyl-8-((R)-1-phenylsulfanyl-ethyl)-5,8-dihydro-[1,2,4]triazolo[1,2-a]pyridazine-1,3-dione 
• 125713-04-4 (4aS,5R,8S,8aR)-5-Methoxymethoxy-8-((R)-1-phenylsulfanyl-ethyl)-4a,5,8,8a-tetrahydro-[1,4]naphthoquinone 
• 125660-41-5 (4aR,5S,8R,8aS)-5-Methoxymethoxy-8-((R)-1-phenylsulfanyl-ethyl)-4a,5,8,8a-tetrahydro-[1,4]naphthoquinone 
• 125660-39-1 4-Methoxymethoxy-2-phenyl-7-((R)-1-phenylsulfanyl-ethyl)-3a,4,7,7a-tetrahydro-isoindole-1,3-dione 
• 125660-36-8 ((2E,4E)-(R)-5-Methoxymethoxy-1-methyl-penta-2,4-dienylsulfanyl)-benzene 

Relevant academic research and scientific papers

Fe(II)-catalyzed imidation of allyl sulfides and subsequent [2,3]- sigmatropic rearrangement. Preparation of α-branched N-tert-butyloxycarbonyl (Boc)-protected N-allylamines

Allyl aryl sulfides 1 and 5 were shown to undergo an imidation/[2,3]- sigmatropic rearrangement reaction upon treatment with N-tert- butyloxycarbonyl azide (BocN3) and catalytic amounts of FeCl2 in CH2Cl2. The N-Boc-protected N-allyl sulfenamides 3 and 21 were obtained in yields between 48 and 75% (12 examples). Whereas the reaction is well suited for the transformation of α-unbranched sulfides to α-branched sulfenamides, the enantiomerically pure α-branched sulfides 10 and 13 reacted sluggishly. The corresponding sulfenamides 22 and 23 were obtained in only moderate enantiomeric excess (36-39% ee). A reaction mechanism is proposed that postulates the intermediacy of an N-Boc-substituted Fe(IV)-nitrene complex 14 acting as the imidation reagent in the catalytic cycle. Possible side reactions are discussed. The benzenesulfenamides 3 were further converted into N-Boc-N-allylamines 4 by removal of the phenylsulfanyl group. Bu3SnH in benzene was found to be the reagent of choice for the deprotection of α- branched amines that bear a secondary allyl substituent (five examples, 71- 93% yield). This method failed for the α-branched amines 3i-k with a tertiary allyl substituent. The phenylsulfanyl group was finally removed with P(OEt)3/NEt3 in CH2Cl2 (three examples, 43-62% yield).

DIELS-ALDER REACTIONS OF ACYCLIC CHIRAL ALKOXY DIENES: OXYGEN VERSUS SULFUR AS AN ALLYLIC DIRECTING GROUP

Facial selectivity in the Diels-Alder reaction of homochiral dienes 1 and 2 was probed using three dienophiles: N-phenylmaleimide (5a), benzoquinone (5b) and 4-phenyl-1,2,4-triazoline-3,5-dione (5c).