Table 1.

Synthesis of Macrocyclic Esters and Amides through Catalytic Z-Selective RCM^a

entry	macrocyclic Z alkene	complex;b loading	condition	conv (%);c yield (%)d	Z:Ec
1		1; 5.0 mol %	ambient	92; 30	17:83
2		2c; 5.0 mol %	ambient	93; 46	15:85
3		6; 3.0 mol %	7.0 torr	63; 49	69:31
4		7; 5.0 mol %	7.0 torr	74; 46	73:27
5		1; 5.0 mol %	ambient	97; 67	7:93
6		2c; 5.0 mol %	ambient	98; 74	7:93
7		6; 3.0 mol %	7.0 torr	74; 50	80:20
8		7; 5.0 mol %	7.0 torr	82; 54	82:18
9		1; 5.0 mol %	ambient	96; 56	21:79
10		2c; 5.0 mol %	ambient	98; 68	15:85
11		6; 3.0 mol %	7.0 torr	72; 50	95:5
12		7; 5.0 mol %	7.0 torr	<20; nd	nd
13		1; 5.0 mol %	ambient	93; 53	56:44
14		2c; 5.0 mol %	ambient	98; 60	66:34
15		6; 3.0 mol %	7.0 torr	81; 69	93:7
16		7; 5.0 mol %	7.0 torr	<20; nd	nd
17		1; 5.0 mol %	ambient	95; 65	23:77
18		2c; 5.0 mol %	ambient	95; 61	24:76
19		6; 3.0 mol %	7.0 torr	85:77	91:9
20		7; 5.0 mol %	7.0 torr	90:78	88:12

^aReactions were carried out in purified toluene (5.0 mM) at 22 °C for one h under an atmosphere of N₂ or under vacuum, as noted; see the Supporting Information for details.

^bComplexes 1, 2c and 7 were prepared prior to use, whereas alkylidene 6 was synthesized in situ from the corresponding bis-pyrrolide and aryl alcohol, proceeding in ~60% yield (3.0 mol % effective catalyst loading). See the Supporting Information for details.

^cConversion and Z:E ratios measured by analysis of 400 MHz 1H NMR spectra of unpurified mixtures; the variance of values are estimated to be ±2%.

^dYield of isolated products (isomeric mixtures) after purification; the variance of values are estimated to be ±5%. nd = not determined.