Asymmetric Synthesis of Diarylmethanols by Chiral Phosphoramide Ligands Catalysts

doi:10.6023/cjoc201902026

Abstract

In order to improve the application of chiral phosphoramide ligands in catalytic asymmetric reactions, thiophosphoramide, which was synthesized from trans-1,2-cyclohexanediamine was used as a catalyst to synthesize chiral diarylmethanol compounds through addition reaction. The catalytic activity of the ligand in the asymmetric addition reaction of the arylalkyl zincs to the aromatic aldehyde can be as high as 94% ee under the optimized reaction conditions in the presence of 30 mol% phosphoramide ligand N-((1R,2R)-2-(isopropylamino)cyclohexyl)-P,P-diphenylphosphinic amide (9c) and the corresponding chiral diarylmethanol compound was obtained with the yields of >90%. Despite the large amount of catalyst, the ligand is very convenient to recycle and reuse in this system. At the same time, the reaction mechanism was speculated, and it is believed that the quaternary transition state and the six-element transition state formed by the reaction process are beneficial to improve the enantioselectivity of the reaction.

Key words: chiral thiophosphoramide ligand, diarylmethanols, asymmetric catalysis

Cite this article

Guo, Qingjun. Asymmetric Synthesis of Diarylmethanols by Chiral Phosphoramide Ligands Catalysts[J]. Chinese Journal of Organic Chemistry, 2019, 39(10): 2912-2919.

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Entry	Ligand	X	NR¹R²	Yield^b/%	ee^c/%
1	7	O	—	83	46
2	8	O	NHⁱPr	89	68
3	9a	O	NHBn	96	29
4	9b	O	NEt₂	84	56
5	9c	O	NHⁱPr	93	78
6	9d	S	NHⁱPr	88	76

Entry	Ligand	X	NR¹R²	Yield^b/%	ee^c/%
1	7	O	—	83	46
2	8	O	NHⁱPr	89	68
3	9a	O	NHBn	96	29
4	9b	O	NEt₂	84	56
5	9c	O	NHⁱPr	93	78
6	9d	S	NHⁱPr	88	76

Entry	9c/ mol%	R	Temp./ ℃	Solvent	Yield^b/%	ee^c/%
1	20	Me	0~25	Toluene	89	74
2	20	Me	0~25	Hexane	85	70
3^d	20	Me	0~25	Hexane/MTBE	53	71
4^d	20	Me	0~25	Hexane/THF	Trace	N.D.^e
5^d	20	Me	0~25	Toluene/hexane	93	78
6^d	20	Me	–10	Toluene/hexane	90	80
7^d	20	Me	–20	Toluene/hexane	90	82
8^d	20	Me	–40	Toluene/hexane	89	86
9^d	20	Et	–40	Toluene/hexane	90	89
10^d^,^f	30	Et	–40	Toluene/hexane	93	94
11^d	40	Et	–40	Toluene/hexane	93	92

Entry	9c/ mol%	R	Temp./ ℃	Solvent	Yield^b/%	ee^c/%
1	20	Me	0~25	Toluene	89	74
2	20	Me	0~25	Hexane	85	70
3^d	20	Me	0~25	Hexane/MTBE	53	71
4^d	20	Me	0~25	Hexane/THF	Trace	N.D.^e
5^d	20	Me	0~25	Toluene/hexane	93	78
6^d	20	Me	–10	Toluene/hexane	90	80
7^d	20	Me	–20	Toluene/hexane	90	82
8^d	20	Me	–40	Toluene/hexane	89	86
9^d	20	Et	–40	Toluene/hexane	90	89
10^d^,^f	30	Et	–40	Toluene/hexane	93	94
11^d	40	Et	–40	Toluene/hexane	93	92

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