Recent Advances in Biomimetic Asymmetric Catalysis for Olefin cis-Dihydroxylation

doi:10.6023/cjoc202504015

Abstract

The development of efficient, selective and environmentally friendly catalytic systems for olefin cis-dihydr- oxylation remains a key objective in synthetic and catalytic chemistry. Naturally occurring Rieske dioxygenases, nonheme iron-dependent enzymes, exemplify this transformation by enabling aerobic, regio-, and stereoselective cis-dihydroxylation of arenes—a critical step in aromatic degradation. These enzymes incorporate both oxygen atoms from O₂ into the cis- dihydrodiol product with high precision. Inspired by the structural and mechanistic features of Rieske dioxygenases, synthetic nonheme iron and manganese complexes have been designed as functional mimics. These complexes effectively mediate asymmetric cis-dihydroxylation of olefins, selectively yielding cis-dihydrodiol products. This review highlights the recent progress in bioinspired nonheme iron and manganese complexes for asymmetric cis-dihydroxylation, along with proposed reaction mechanisms.

Key words: biomimetic catalysis, Rieske dioxygenases, asymmetric cis-dihydroxylation, high-valent metal-oxygen species, nonheme metal complexes

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Xin Liu, Shixin Zheng, Huajie Zhao, Jie Chen, Bin Wang. Recent Advances in Biomimetic Asymmetric Catalysis for Olefin cis-Dihydroxylation[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4257-4270.

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Fig. & Tab. 20

Figure 1. Enantioenriched cis-1,2-diols and Sharpless asymmetric dihydroxylation

Figure 2. (A) Electron transfer chain in NDO, (B) schematic structure of the active site of a Rieske dioxygenase, and (C) iron active site in NDO (Pseudomonas putida) during catalysis [left to right: Substrate-bound (PDB ID: 1O7G), O2-bound (PDB ID: 1O7M), and product-bound (PDB ID: 1O7P) states; Color code: violet=Fe, blue=N, red=O, gold=C]

Scheme 1. Proposed mechanistic pathways for NDO

Scheme 2. The first example of a nonheme iron complex that catalyzes olefin cis-dihydroxylation

Entry	Substrate	TON^a			RC^b/%
Entry	Substrate	cis-Diol	Epoxide	cis-Diol/Epoxide	RC^b/%
1	Styrene	8.0	0.1	80	—
2	1-Octene	7.6	0.1	76	—
3	Cyclohexene	6.2	0.7	9	—
4	cis-2-Heptene	4.9	0.7	7	99
5	trans-2-Heptene	4.9	0.5	10	˃ 99
6	Ethyl trans-crotonate	7.4	—	˃ 100	—
7	tert-Butyl acrylate	5.5	—	˃ 100	—
8	Dimethyl fumarate	5.3	—	˃ 100	—

Table 1. Catalytic oxidation of various olefins by 2 under substrate-limiting conditions

Entry	Substrate	Yield^a/%			RC^b/%
Entry	Substrate	cis-Diol	Epoxide	cis-Diol/Epoxide	RC^b/%
1	1-Octene	67	20	3.4	—
2	1-Decene	62	18	3.4	—
3	Vinylcyclohexane	57	16	3.6	—
4	Cyclohexene	45	30	1.5	—
5	cis-2-Heptene	60	20	3.0	97
6	trans-2-Heptene	61	14	4.4	99

Table 2. Catalytic oxidation of various olefins by 3 under substrate-limiting conditions

Figure 3. Nonheme iron complexes utilized in asymmetric cis-dihydroxylation of olefins

Entry	Complex	Labile site	Substrate	TON^a			ee/%
Entry	Complex	Labile site	Substrate	cis-Diol	Epoxide	cis-Diol/Epoxide	ee/%
1	4^b	Two cis-α	trans-2-Heptene	0.3	5.4	0.055	29
2	5^c	Two cis-β	trans-2-Heptene	7.5	2.4	3.1	79
3			cis-2-Heptene	7.8	4.5	1.7	9
4			1-Octene	8.1	1.3	6.2	60
5			tert-Butyl acrylate	10	0.5	20	23
6	6^d	Two cis-α	trans-2-Heptene	1.1	5.1	0.22	38
7			1-Octene	1.7	2.6	0.67	11
8			tert-Butyl acrylate	0.1	3.0	0.033	—
9	7^d	Two cis-α	trans-2-Heptene	5.2	0.2	26	97
10			cis-2-Heptene	3.4	0.6	5.7	11
11			1-Octene	6.4	0.1	64	76
12			Styrene	6.5	<0.1	>65	15
13			tert-Butyl acrylate	4.0	<0.1	>40	68
14			Ethyl trans-crotonate	7.5	0.1	>75	78
15	8^d	Two cis-α	trans-2-Heptene	3.6	0.9	4	78
16			1-Octene	4.6	0.5	9	29
17			tert-Butyl acrylate	2.7	<0.1	>27	23

Table 3. Nonheme iron-catalyzed asymmetric cis-dihydroxylation in the presence of a large excess of olefins

Figure 4. Coordination modes for octahedral stereogenic-at-iron complexes with linear N4 ligand

Scheme 3. Nonheme iron-catalyzed asymmetric cis-dihydroxy- lation of olefins with H2O2 via a putative FeIII—OOH intermediate

Scheme 4. Proposed pathways for olefin epoxidation and cis-dihydroxylation mediated by nonheme iron complex and H2O2 (Sol=CH3CN or CH3OH)

Scheme 5. Nonheme iron-catalyzed asymmetric cis-dihydroxy- lation of trisubstituted olefins

Figure 5. Nonheme manganese complexes utilized in asymmetric cis-dihydroxylation of olefins

Scheme 6. Nonheme iron-catalyzed asymmetric cis-dihydroxy- lation by modulating the counterions of the ferrous complex

Scheme 7. Asymmetric cis-dihydroxylation with a dinuclear Mn(III) complex containing chiral carboxylato ligands

Scheme 8. Mononuclear manganese-catalyzed asymmetric cis- dihydroxylation with oxone

Scheme 9. Mononuclear manganese-catalyzed asymmetric cis- dihydroxylation with H2O2

Scheme 10. Mononuclear manganese-catalyzed asymmetric cis-dihydroxylation with KHSO5

Figure 6. DFT-computed Gibbs energy profiles (in kcal mol−1) for water-assisted formation of HO—MnV=O from MnIII(H2O)- (OOH)

Scheme 11. Mechanistic proposal for asymmetric cis-dihydroxylation catalyzed by mononuclear nonheme Mn complex

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