Table 1.

Synthesis of natural product‐like macrocycles (see Figure 2; Products had R¹=^FDIPES; R², R³=Ns; R⁴=TBS unless stated).

Building blocks	Attachment of terminating building block[a]	Metathesis[c]
	Mass recovery (purity)[b]	Product	Yield [%][d]	E/Z [e]
13, 9	66 (95)	24 [f]	33[g]	60:40
13, 10	77 (93)	25 [h]	56	65:35
13, 11	57[d]	23 [f]	84[g]	30:70
13, 12	93 (>95)	26	76	>98:<2
14, 9	>98 (59)	27	56	60:40
14, 10	76 (94)	28 [h]	88	[i]
14, 11	93 (95)	29 [h]	78	15:85
14, 12	>98 (83)	30 [h]	47	[i]
15, 9	90 (93)	21 [f]	34[g]	65:35
15, 10	70[d]	31	60	>98:<2
16, 9	97[d]	32	88	>98:<2
16, 10	95[d]	33	75	>98:<2
16, 11	93[d]	34	61	>98:<2
16, 12	>98[d]	35	98	70:30
17, 9	92[d]	36	76	25:75
17, 10	90[d]	37	78	70:30
17, 12	99[d]	38 [j]	55 (E); 15 (Z)

[a] Method A: PPh₃, DEAD, CH₂Cl₂ then F‐SPE. [b] Mass recovery (and purity determined by 500 MHz ¹H NMR spectroscopy) after purification by F‐SPE alone. [c] Method C: 2 or 5 mol % Hoveyda‐Grubbs second generation catalyst, 0, 4 or 10 mol % 1,4‐benzoquinone, MTBE, 55 °C then P(CH₂OH)₃, Et₃N, silica (see Supporting Information). [d] Yield after column chromatography. [e] Determined by 500 MHz ¹H NMR spectroscopy. [f] The product had R¹=^FDIPES; R²=R³=H after desulfonylation. [g] Yield over two steps after desulfoylation with PhSH, K₂CO₃. [h] The geometric isomers were separable after subsequent desulfonylation. [i] Not determined at this stage; after desulfonylation, 28 and 30 were separable geometric isomers. [j] The geometrical isomers were separable.