空间受阻离子对催化缩醛及缩酮高效脱保护反应

doi:10.6023/cjoc202604046

摘要/Abstract

缩醛和缩酮结构是羰基官能团的重要保护基之一, 在有机合成化学中应用广泛. 报道了空间受阻三芳基碳正离子离子对催化缩醛与缩酮的高效脱保护反应. 在温和且无金属的反应条件下, 脱保护反应时间仅需20 min即可完成, 且具有优异的官能团耐受性, 以高产率(最高达98%)得到各类羰基化合物, 底物范围涵盖各种类型的醛、酮以及复杂天然产物分子. 此外, 该脱保护策略也被成功应用于克级规模制备, 反应操作简单, 具有较强的实用性.

关键词: 无金属催化, 空间受阻离子对, 缩醛缩酮脱保护

Acetals and ketals are among the most important protecting groups for carbonyl groups and are widely used in synthetic chemistry. An efficient deprotection reaction for cyclic acetals and ketals catalyzed by triaryl carbenium ion-pair is presented. Under mild and metal-free conditions within only 20 min, a wide range of carbonyl products were obtained in high yields (up to 98%) with excellent functional group tolerance, including aldehydes, ketones and natural products. Moreover, this deprotection process is applicable to gram-scale synthesis, featuring operational simplicity and practical utility.

Key words: metal-free catalysis, frustrated ion-pair, deprotection of acetals and ketals

引用此文

杨超, 李若琪, 张羽, 邹明, 陈朋, 贾振华. 空间受阻离子对催化缩醛及缩酮高效脱保护反应[J]. 有机化学, 2026, 46(10): 4067-4076.

Chao Yang, Ruoqi Li, Yu Zhang, Ming Zou, Peng Chen, Zhenhua Jia. Efficient Deprotection of Acetals and Ketals Catalyzed by Frustrated Ion Pairs[J]. Chinese Journal of Organic Chemistry, 2026, 46(10): 4067-4076.

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参考文献 38

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Entry	Catalyst	Catalyst loading	Solvents (V∶V)	Time/min	Yield^b/%
1	—	—	H₂O/MeCN (4∶1)	20	n.r
2	Ion-pair 1	5 mol%	H₂O/MeCN (4∶1)	20	n.r
3	Ion-pair 2	5 mol%	H₂O/MeCN (4∶1)	20	n.r
4	Ion-pair 3	5 mol%	H₂O/MeCN (4∶1)	20	10
5	Ion-pair 4	5 mol%	H₂O/MeCN (4∶1)	20	n.r
6	Ion-pair 5	5 mol%	H₂O/MeCN (4∶1)	20	12
7	B(C₆F₅)₃	5 mol%	H₂O/MeCN (4∶1)	20	42
8	Ion-pair 7	5 mol%	H₂O/MeCN (4∶1)	20	76
9	Ion-pair 8	5 mol%	H₂O/MeCN (4∶1)	20	90
10	Ion-pair 9	5 mol%	H₂O/MeCN (4∶1)	20	10
11	Ion-pair 10	5 mol%	H₂O/MeCN (4∶1)	20	11
12	Ion-pair 8	5 mol%	H₂O	20	n.r
13	Ion-pair 8	5 mol%	H₂O/MeCN (9∶1)	20	68
14	Ion-pair 8	5 mol%	H₂O/THF (9∶1)	20	40
15	Ion-pair 8	5 mol%	H₂O/DMSO (9∶1)	20	90
16	Ion-pair 8	5 mol%	H₂O/HFIP (9∶1)	20	98 (92)^c
17	Ion-pair 8	5 mol%	H₂O/HFIP (9∶1)	15	88
18	Ion-pair 8	1 mol%	H₂O/HFIP (9∶1)	20	82
19	Ion-pair 8	5 mol%	H₂O/HFIP (9∶1)	20	96^d

Entry	Catalyst	Catalyst loading	Solvents (V∶V)	Time/min	Yield^b/%
1	—	—	H₂O/MeCN (4∶1)	20	n.r
2	Ion-pair 1	5 mol%	H₂O/MeCN (4∶1)	20	n.r
3	Ion-pair 2	5 mol%	H₂O/MeCN (4∶1)	20	n.r
4	Ion-pair 3	5 mol%	H₂O/MeCN (4∶1)	20	10
5	Ion-pair 4	5 mol%	H₂O/MeCN (4∶1)	20	n.r
6	Ion-pair 5	5 mol%	H₂O/MeCN (4∶1)	20	12
7	B(C₆F₅)₃	5 mol%	H₂O/MeCN (4∶1)	20	42
8	Ion-pair 7	5 mol%	H₂O/MeCN (4∶1)	20	76
9	Ion-pair 8	5 mol%	H₂O/MeCN (4∶1)	20	90
10	Ion-pair 9	5 mol%	H₂O/MeCN (4∶1)	20	10
11	Ion-pair 10	5 mol%	H₂O/MeCN (4∶1)	20	11
12	Ion-pair 8	5 mol%	H₂O	20	n.r
13	Ion-pair 8	5 mol%	H₂O/MeCN (9∶1)	20	68
14	Ion-pair 8	5 mol%	H₂O/THF (9∶1)	20	40
15	Ion-pair 8	5 mol%	H₂O/DMSO (9∶1)	20	90
16	Ion-pair 8	5 mol%	H₂O/HFIP (9∶1)	20	98 (92)^c
17	Ion-pair 8	5 mol%	H₂O/HFIP (9∶1)	15	88
18	Ion-pair 8	1 mol%	H₂O/HFIP (9∶1)	20	82
19	Ion-pair 8	5 mol%	H₂O/HFIP (9∶1)	20	96^d