Lanthanum Silylamide-Catalyzed Synthesis of Enol Phosphates

doi:10.6023/cjoc202306012

Abstract

Enol phosphate has important applicative value in many fields. The development of a catalytic and selective method for the synthesis of enol phosphate is of great significance. The reaction of 4-oxo-4-arylbut-2-enoate and diethyl phosphite catalyzed by lanthanum silylamide [(Me₃Si)₂N]₃La(μ-Cl)Li(THF)₃ is developed, which provides a series of enol phosphates in cis-configuration. Research on the mechanism indicates that the reaction undergoes a relatively rare [1,4]-phospha-Brook rearrangement. The reaction has advantages of ready availability of catalyst and high selectivity for alkenyl configuration, providing an efficient method for the synthesis of enol phosphates.

Key words: enol phosphate, lanthanide silylamide, catalysis, phospha-Brook rearrangement, stereoselectivity

Cite this article

Kang Pan, Fan Xu. Lanthanum Silylamide-Catalyzed Synthesis of Enol Phosphates[J]. Chinese Journal of Organic Chemistry, 2023, 43(12): 4261-4267.

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Entry	Ar	Yield/%
1	Ph	71
2	p-FC₆H₄	68
3	p-ClC₆H₄	65
4	p-BrC₆H₄	69
5	m-ClC₆H₄	56
6	o-ClC₆H₄	42
7	p-CH₃C₆H₄	55
8	p-CH₃OC₆H₄	32
9	m-CH₃OC₆H₄	64

Entry	Ar	Yield/%
1	Ph	71
2	p-FC₆H₄	68
3	p-ClC₆H₄	65
4	p-BrC₆H₄	69
5	m-ClC₆H₄	56
6	o-ClC₆H₄	42
7	p-CH₃C₆H₄	55
8	p-CH₃OC₆H₄	32
9	m-CH₃OC₆H₄	64

硅氨基镧化合物催化合成磷酸烯醇酯