铑催化2-烯基苯酚与炔烃的对映体选择性螺环化反应

doi:10.6023/cjoc202303021

摘要/Abstract

发展了铑催化2-烯基苯酚与炔烃的对映选择性螺环化反应. 在5 mol% 1,1'-联二萘酚(BINOL)衍生的环戊二烯铑络合物[(R)-CpRh1]和2 equiv.的醋酸铜存在下, C—H活化/螺环化反应可以高达84%收率和81% ee对映选择性获得手性螺环己烯酮化合物. 该反应条件温和, 具有良好的官能团耐受性.

关键词: 2-烯基苯酚, 炔烃, 环戊二烯铑络合物, 螺环化反应, 螺环己烯酮

Rh-catalyzed enantioselective spiroannulation of 2-alkenylphenols with alkynes was developed. In the presence of 5 mol% BINOL-derived (BINOL: 1,1'-bi-2,2'-naphthol) cyclopentadiene-Rh complex [(R)-CpRh1] and 2 equiv. of Cu(O- Ac)₂, the C—H activation/annulation reaction proceeded smoothly to afford a wide range of enantioenriched spirocyclohexenones in up to 84% yield and 81% ee. This reaction features mild reaction conditions and good functional group tolerance.

Key words: 2‑alkenylphenol, alkyne, cyclopentadiene-Rh complex, spiroannulation, spirocyclohexenone

引用此文

张素珍, 张文文, 杨慧, 顾庆, 游书力. 铑催化2-烯基苯酚与炔烃的对映体选择性螺环化反应[J]. 有机化学, 2023, 43(8): 2926-2933.

Suzhen Zhang, Wenwen Zhang, Hui Yang, Qing Gu, Shuli You. Rhodium-Catalyzed Enantioselective Spiroannulation of 2-Alkenylphenols with Alkynes[J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2926-2933.

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图/表 4

图1. 萘酚/苯酚与炔烃的对映选择性氧化环化反应

Figure 1. Enantioselective oxidative cyclization of naphthol/phenol with alkyne

Entry	[Rh]	Solvent	Yield^b/%	ee^c/%
1	(R)-CpRh1	CH₃CN	48	74
2	(R)-CpRh2	CH₃CN	60	40
3	(R)-CpRh3	CH₃CN	50	60
4	(R)-CpRh4	CH₃CN	39	56
5	(R)-CpRh5	CH₃CN	8	39
6	(S)-SCpRh1	CH₃CN	18	54
7	(S)-SCpRh2	CH₃CN	60	38
8^d	(R)-CpRh1	CH₃CN	52	76
9^d	(R)-CpRh1	^tAmylOH	60	75
10^d	(R)-CpRh1	1,4-Dioxane	14	83
11^d	(R)-CpRh1	THF	21	80
12^d	(R)-CpRh1	DMF	31	70
13^d	(R)-CpRh1	1,4-Dioxane/^tAmylOH	42	77
14^d	(R)-CpRh1	THF/^tAmylOH	52	76
15^d	(R)-CpRh1	DMF/^tAmylOH	81 (77^e)	81

表1. C—H活化/环化反应条件优化a

Table 1. Optimization of the C—H activation/annulation reaction conditions

图式1. 铑催化2-烯基酚与炔烃的对映体选择性螺环化反应

Scheme 1. Rhodium-catalyzed enantioselective spiroannulation of 2?alkenylphenols with alkynes Reaction conditions: 1 (0.2 mmol), 2 (1.5 equiv.), (R)-CpRh1 (5 mol%), Cu(OAc)2 (2.0 equiv.), DMF/tAmylOH (2 mL), argon, 60 ℃

图2. C—H 活化/螺环化反应可能的催化循环

Figure 2. Proposed catalytic cycle for C—H activation/spiroannulation reaction

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