Chapter 1 overviews the relationship between cyclophanes and natural product synthesis. The ultimate objective of the present study is to seek a potential employment of cyclophane intermediates en route to complex natural product skeleta. Chapter 2 describes the synthesis of 2,11-dithia[3.3]metacyclophanes bearing sulfur-containing groups at the 6 and 15 positions. Chapter 3 details the synthesis of some (1,3)indolophanes and the analysis of their conformational behavior. Further study of the hydroboration/Suzuki-Miyaura strategy, as an expedient entry into [3.3]cyclophanes, is also reported. Chapter 4 presents a synthesis of an indolopyridazinophane, relying on the hydroboration/Suzuki-Miyaura strategy. The subsequent transannular inverse electron demand Diels-Alder (IEDDA) reaction of the resulting cyclophane has established efficient access to a highly compact pentacyclic indoloid skeleton. Chapter 5 demonstrates a formal total synthesis of (±)-strychnine, one of the most complex natural products for its size, by preparing Rawal's key pentacyclic intermediate via the cyclophane approach.