Reactivity and Utility of Allenylphosphonates: Formation of a Novel Hydroperoxide and Propargylic Alcohol and Facile Thiol Addition under Catalyst-Free, Solvent-Free Conditions

 

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Abstract

2-(Propa-1,2-dienyl)-, 2-(buta-1,2-dienyl)-, and 2-(3-methylbuta-1,2-dienyl)-substituted 5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxides 1a-c react readily upon heating with thiols under catalyst-free, base-free, and solvent-free conditions to give sulfanyl-substituted phosphonates. The reaction undergoes to essential completion within 15 minutes under microwave radiation. While 1a,b react with 4-chlorothiophenol to afford both 2-[2-(4-chlorophenylsulfanyl)prop-1-enyl]- 12 and 2-[2-(4-chlorophenylsulfanyl)prop-2-enyl]-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxides 13, 1c gives 2-[2-(4-chlorophenylsulfanyl)-3-methylbut-2-enyl]-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (13d) regioselectively. Molecular oxygen undergoes a novel reaction with the allene 1c to give propargylic alcohol 2-(3-hydroxy-3-methylbut-1-ynyl)-5,5-dimethyl-1,3,2-dioxaphosphinane 2-oxide (16) via the corresponding hydroperoxide; the structures of these were confirmed by X-ray crystallography. The synthetic utility of the sulfanyl-substituted allyphosphonate 13d in the Horner-Wadsworth-Emmons reaction to afford synthetically valuable sulfanyl-substituted buta-1,3-dienes and a conjugated triene is demonstrated.

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The ¹H NMR spectrum of this mixture showed peaks at δ = 3.40 (d, J = 22.0 Hz), in addition to those for 12a and 1a. There was also an additional minor peak in the initial stages in the ³¹P NMR at δ = 23.9 (unassigned).

Compound 15 was more difficult to obtain in a pure form, probably because of conversion into 16.

When we tried to separate this compound from 5,5-diethyl-2-(3-methylbuta-1,2-dienyl)-1,3,2-dioxaphosphinane 2-oxide using column chromatography, a small quantity of an additional species [δ(P) -12.2] was noticed in a few fractions.

IR (KBr): 3399, 2928, 1570, 1335, 1206, 1057, 1005 cm^-1; ¹H NMR (400 MHz, CDCl₃): δ = 0.99 and 1.10 (2 s, 6 H, 2 CH ₃), 2.01-2.06 [2 m due to coupling to phosphorus and CH₂ with J <5.0 Hz, 6 H, =C(CH ₃)₂], 3.34 (dd, J ˜4.0 Hz, J ˜20.6 Hz, 2 H, PCH ₂), 3.79-4.95 (m, 9 H, CH ₂OH, CHCH₂OH, 2 CHOH, OCH ₂), 5.90 (d, J ˜7.0 Hz, OCHN of ribose), 8.13 (s, 1 H, nucleobase-H), 8.62 (s, 1 H, Nucleobase-H); LC-MS showed a peak at m/z 503.