Conspectus Developing new methods that enable the synthesis of new and complex molecules with complete control of their 3-D shape is central to the advancement of synthetic chemistry with applications spanning from medicine to materials. Our approach consists of the iterative combination of small building blocks through the use of boron chemistry to essentially “grow” molecules. This approach, which we term assembly-line synthesis (ALS), resembles the way that nature assembles natural products (e.g., the polyketide synthase machinery) and has the advantage that many structural variations can be easily introduced and the products can be evaluated in structural or biological contexts. Chiral boronic esters have been recognized as valuable building blocks due to their unique chemical properties. They are both chemically and configurationally stable, and they can be prepared with very high levels of enantioselectivity. Additionally they undergo a broad array of transformations that lead to the stereocontrolled formation of C–C and C–X (X = heteroatom) bonds. This versatility makes boronic acids ideal building blocks for iterative molecular assembly. A powerful reaction platform for chemical diversification using chiral boronic esters is their homologation using lithium carbenoids via 1,2-metalate rearrangement. In the 1980s, Matteson described the use of boronic esters bearing a chiral diol in a two-step homologation process with dichloromethyl lithium and Grignard reagents (substrate-controlled approach). We have focused on reagent control and have found that Hoppe’s chiral lithiated carbamates can be used as carbenoid equivalents in conjunction with achiral boronic esters. This reagent-controlled process offers many advantages due to the easy access of both the chiral lithiated carbamates and stable boronic esters. The carbamates can be derived from primary or secondary alcohols, and a broad range of functionalized boronic esters and boranes can be employed. Multiple homologations can be carried out in a one-pot sequence thereby streamlining the process to a single operation. This methodology has enabled the synthesis of many molecules containing multiple contiguous stereogenic centers with exquisite 3-D control. In this Account, we trace our own studies to establish the lithiation–borylation methodology and describe selected synthetic applications.