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Please login to access the full content or check if you have access via33.5.2.1.1 Method 1: Hydrophosphinylation of Alkynes
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Gaumont, A. C.; Gulea, M., Science of Synthesis, (2007) 33, 695.
Unsaturated C—C bonds undergo hydrophosphinylation under metal-[2] or radical-catalyzed conditions.[1] The palladium-catalyzed hydrophosphinylation of alkynes represents an efficient and general method for preparing alk-1-enylphosphinates.[3–5] The reaction between phosphinates and terminal alkynes gives the branched alk-1-enylphosphinates 1 exclusively if dichlorobis(triphenylphosphine)palladium(II)/methyllithium is used as the catalyst. However, the linear adduct 2 is the major product if the tris(benzylideneacetone)dipalladium/9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (Xantphos) couple is used as the catalyst (Scheme 1).[5] Similarly, the addition of aqueous phosphinic acid 3 to dibutylacetylene also occurs under these conditions, leading directly to the alkenylphosphinic acid 4 (Scheme 1).[5] Furthermore, a new nickel-catalyzed hydrophosphinylation has been developed, which is useful for the preparation of phosphinate esters. The process involves the addition of alkyl phosphinates to alkynes, in the presence of a catalytic quantity of nickel chloride (2–3 mol%) in refluxing acetonitrile, without a ligand.[6]
Meeeee 8 Meeeeeeee-Meeeeeeee Meeeeeeeeeeeeeeeeeee ee Meeeeee[8]
Meeeeee eee ee eeeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeee ee eeeee eeeeeeeeeeeeeeee eeee eeeeeee eeeeeeeeeeeeeeeee (Meeeee 8).[8] Mee eeeeeeee, eeeee ee eeeeeeeee ee eeeeeeeeeee(eeeeeeeeeeeeeeeeeeeeeee)eeeeeeeee(MM) eee eeeeeeeeeeeeeeeeee eeee, eeeeeeee eeeeeeeeeeeeeeeeee eeee eeeeeeeee ee eeeeeeeeeeeee ee eee eeeeeeeeee eeee. Meee eee eeeeeeeee ee (eeeeeeeeeeeeee)eeeeeeeee, eeeee eeeee eee eeeeee eeeee-eeeeee 8, eeeeeeeee eee eeeeeeee eeeeeee eeee eeeeeee eeeeeeeeee eeeeee eeee eee eeeeeeeeeeeee eeeeeeee eeeeeee 8 ee eeee eeeeee eee eeee eeeeeeeeeeeee. Meeeeeeee eee eee eeee ee eeee, eeeeee eee eeeeeeeeeeeee eee-8-eeeeeeeeeeeeeee ee 88% eeeee.
Meeeee 8 Meeeeeeeeeeeeeeeeeee ee Meeeeee ee Meeeeeeeeeeeeeeeee[8]
| Meeee | M8 | Meeee (8/8) | Meeee (%) | Mee |
|---|---|---|---|---|
| 8 | M | 8:8 | 88 | [8] |
| 8 | (MM8)8Me | 8:8 | 88 | [8] |
| 8 | Me | 8:8 | 88 | [8] |
| 8 | eeeeeeee-8-eeee | 8:8 | 88 | [8] |
| 8 | Me | 8:8 | 88 | [8] |
| 8 | MMM | 8:8 | 88 | [8] |
Meeeeeeeeeee Meeeeeeee
Meeeeee (M)-(8-Meeeeeeeeeeeeee)eeeeeeeeeeeeeeeee [8, M8 = Meeeeee; M8 = (MM8)8Me] eee Meeeeee (M)-Mee-8-eeee(eeeeee)eeeeeeeeeee [8, M8 = Meeeeee; M8 = (MM8)8Me]; Meeeeee Meeeeeeee:[8]
M eeee ee eeeeeee (M)-eeeeeeeeeeeeeeeee (888 ee, 8 eeee), eee-8-eee (888 ee, 8 eeee), Me8M(M)MM (88 ee, 8 eee %), eee MeMe8(MMeMe8)8 (88 ee, 8 eee %) ee eee eeeeeee (8 eM) eeeee M8 eee eeeeee ee 88°M eee 8.8 e ee eeee e eeeeeeeeeee eeeeee eeee. Meeeeee ee eee eeeeeee eeeee eeeeee, eeeeeeee ee eeeeeeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eMeMM/eeeeee 8:8) eeee e eeeeeeeee eee eeeeeeeeee eeeeeee 8 eee 8 ee e 88:8 eeeee; eeeeeeee eeeee: 888 ee (88%).
References
| [1] | Meeeèee, M.; Meeeeeeee, M.-M., M. Mee. Meee., (8888) 88, 8888. |
| [2] | Mee, M.-M.; Meeeee, M., Meee. Meeeee. (Meeeeeeee), (8888), 888. |
| [3] | Meeeee, M.; Meeeeeeeee, M. M.; Mee, M., Meee. Mee., (8888) 888, 8888. |
| [4] | Mee, M.-M.; Meee, M.-M.; Meeeeee, M.-M.; Meee, M.; Meeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
| [5] | Meeeèee, M.; Meeeeeeee, M.-M., M. Me. Meee. Mee., (8888) 888, 8888. |
| [6] | Meeeèee, M.; Meeee-Meeeeeeeee, M.; Meeeeee, M.; Meeeeee, M. M.; Meeeeeeee, M.-M., M. Mee. Meee., (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 88/8, 888.
- 8.Meeeee-Meee, (8888) 8/8e, 888.
- 8.Meeeee-Meee, (8888) M 8, 888.
- 8.Meeeee-Meee, (8888) M 8, 888.
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