Correction to “Ligand Effects in Regio‐ and Enantioselective Cobalt‐Catalyzed Intramolecular [4 + 2]‐ and [2 + 2]‐Cycloaddition Reactions of Unactivated 1,3‐Diene‐8‐ynes and 1,3‐Diene‐8‐enes”

K. K. Ghosh, R. Chowdhury, J. P. Gordon, T. V. RajanBabu, “Ligand Effects in Regio‐ and Enantioselective Cobalt‐Catalyzed Intramolecular [4+2]‐ and [2+2]‐Cycloaddition Reactions of Unactivated 1,3‐Diene‐8‐ynes and 1,3‐Diene‐8‐enes”, Angewandte Chemie International Edition 64 (2025): e202515154

Because of an inadvertent error in the configurations of the Ph‐bearing starting material 3b shown in Equation 3, some of the data in Table 2 (entries 10–15) require corrections. The two isomeric 3b diene‐enes, (2E,4E)‐3b and (2Z,4E)‐3b, differing in the configuration of the internal double bond, were used in these entries, even though in the original Equation 3, the starting material 3b was depicted without any configurational assignments, thus implying a (2E,4E) configuration. The two isomeric compounds were prepared via two routes (Equations 3a and 3b). The (2E,4E)‐3b was prepared via Mitsunobu coupling of N‐allyl‐N‐(4‐methyl)benzene sulfonamide and (2E,4E)‐5‐phenyl‐penta‐2,4‐dienol (p. S8 and S14). The (2Z,4E)‐3b was prepared via coupling of 4‐methyl‐N‐((2Z,4E)‐5‐phenylpenta‐2,4‐dien‐1‐yl)‐benzenesulfonamide and allyl alcohol (p. S4 and S14).

TABLE 2.

Effect of chiral ligands on yield and enantioselectivity of [2 + 2]‐ and [4 + 2]‐cycloaddition reactions of 1,3‐diene‐enes (2E, 4E)‐3b, and (2Z, 4E)‐3b.

Entry	Ligand	Substrate	Yield	Product	er (configuration)
(Entries 1–9): Me/3a (2E,4E) no changes in substrates/ligands/products					‐
(Entries 10–15): Ph/3b (2Z,4E)
10	L1	(2E,4E)‐3b	74%	4b (only)	99:1 (3aS, 5R, 7aR)
12	L3	(2Z,4E)‐3b	71%	5b	95:5 (1S, 5R, 6S)
13	L4	(2E,4E)‐3b	40%	4b (only)	97:3 (3aR, 5S, 7aS)
14	L5	(2Z,4E)‐3b	64%	5b	79:21
15	L6	(2Z,4E)‐3b	14%	5b (only)	55:45

The starting material, (2E,4E)‐3b, led to the [4 + 2]‐cycloaddition product 4b (p. S43). This product is configurationally similar to the product 4a (X‐ray) from starting material (2E,4E)‐3a, which originated from (E,E)‐sorbic alcohol, (2E,4E)‐hexa‐2,4‐dien‐1‐ol (p. S8, and S42). Ligands L1 and L4 delivered the product 4b from the diene‐ene (2E,4E)‐3b with the best enantioselectivity (entries 10 and 13). Ligand L3 delivered the product 5b with the best enantioselectivity from the diene‐ene, (2Z, 4E)‐3b (entry 12, p. S46). Ligands L5 and L6 also gave 5b, albeit in lower er's. Thus, the outcomes of these [4 + 2]‐and [2 + 2]‐cycloadditions of diene‐ene depend on the configuration of the internal double bond of the diene‐ene. The corrected Table 2 showing these results is shown above (p. S28):

The scope and substrate dependence on the intramolecular [4 + 2]‐ and [2 + 2]‐cycloadditions of 1,3‐diene‐enes is outlined in modified‐Equation 4 of Figure 6 (below). The starting configurations of the diene‐enes in Equation 4 (Figure 6) should be depicted as (2E,4E) or (2Z,4E). The diene‐enes for the [4 + 2]‐adducts (4a–4f) originated from (2E,4E)‐diene precursors (as in example, Equation 3a) and the diene‐enes for the [2 + 2]‐adducts (5b–5g) came from a corresponding (2Z,4E)‐diene precursors (as in Equation 3b, See Supporting Information for details). The narrative in the publication, p. 6, column 2, para 1, should be revised to indicate use of (2Z,4E)‐substrate 3 for products 5b–5g (p. S28 and p. S46–p. S51).

Modified Equation 4 in Figure 6. Scope of intramolecular [4 + 2]‐ and [2 + 2]‐cycloadditions of 1,3‐diene‐enes.

To be consistent with these observations, the proposed mechanism (original Figure 8) should also include the (2Z,4E)‐diene‐ene as the starting material, giving the [2 + 2]‐cycloadduct.

Finally, the starting enynes 1i and 1l for the synthesis of 2i (p. S36) and 2l (p. S38) original Figure 4) were derived from (2Z,4E)‐diene‐yne precursors, and, thus the configurations of these products (as yet undetermined) will be different from what is recorded in Figure 4 based on the analogy to the X‐ray crystallographic structure of 2d, which originated from a (2E,4E)‐diene‐yne precursor.

The original Supporting Material has been updated (anie71911‐sup‐0001‐SuppMat.pdf), which contains data supporting all studies in this publication. We like to thank Mengmeng Wang (Zhengzhou University) for alerting us to a discrepency which initiated this revision.

We apologize for this error.

Supporting information

Supporting File: anie71911‐sup‐0001‐SuppMat.pdf.